Metal organic framework

Abstract

The present invention relates to metal organic framework(s) (MOF(s)), compositions comprising said MOF(s), MOF body or bodies comprising said MOF(s), MOF-coated non-MOF substrate body or bodies comprising said MOF(s), structured adsorbent beds comprising said MOF(s), methods of producing said MOF(s) and uses of said MOF(s).

Description

Metal Organic FrameworkField of the Invention

[0001] The present invention relates to metal organic framework(s) (MOF(s)), compositions comprising said MOF(s), MOF body or bodies comprising said MOF(s), MOF-coated non-MOF substrate body or bodies comprising said MOF(s), structured adsorbent beds comprising said MOF(s), methods of producing said MOF(s) and uses of said MOF(s).Background of the Invention

[0002] Greenhouse gases, such as carbon dioxide and methane, are harmful to the planet and contribute to climate change. Means of capturing greenhouse gases, particularly from industrial sources, are required to mitigate global greenhouse gas emissions. In addition, means to address other consequences of climate change are also required such as improved means of storing hydrogen - as a non-carbon dioxide emitting fuel - and atmospheric water harvesting.

[0003] Various materials, including some metal organic frameworks, can be used to capture CO2 from industrial emissions, such as flue gases. Metal-organic frameworks can also be used as sorbent materials for hydrogen storage. Capture of CO2 from flue gases is often industrially, environmentally and economically preferred due to the higher concentration of CO2 in the flue gases and the consequent ease of carbon capture in these conditions.

[0004] Metal organic frameworks (MOFs) are a class of porous polymers consisting of metal ions (inorganic nodes) coordinated to and connected by organic ligands. MOF structures are typically highly porous and the range of possible ligands and metals means that they can be optimised to be good sorbents for specific materials, including gases such as CO2, hydrogen, methane and water. MOFs have been shown to have high potential in various applications, for example carbon capture, gas separation and storage, sensing and catalysis. However, there are often limitations to their use in large scale industrial processes, such as carbon capture, hydrogen storage and water harvesting. Some MOFs have limited moisture and thermalstability, poor selectivity for the target adsorbent, poor total sorbent capacity or require expensive raw materials.

[0005] These limitations are especially relevant for MOFs used for carbon capture, hydrogen storage and other large-scale industrial gas separation processes, given the scale of the quantities involved and the conditions under which they operate. Such MOFs need to comprise a careful balance of properties, including adsorbent (e.g. CO2) selectivity, to address these limitations. In addition, such MOFs ideally need to be easy to synthesise, as well as to form into coatings and body(ies) (monolith(s)), for example.

[0006] Thus, there is a continual need for new, selective MOFs having porosity profiles, stability, improved selectivity, adsorbent capabilities suitable for carbon dioxide capture - especially from flue gases - as well as other gas separation and storage applications. These MOFs and compositions comprising the MOFs need to be able to operate effectively at the use conditions. Furthermore, the MOFs ideally need to be straightforward to synthesize using readily available raw materials. The present invention addresses these, and other issues.Summary of the Invention

[0007] Accordingly, in a first aspect, the invention provides a metal organic framework (MOF) comprising i. a plurality of metal ions, each of the plurality of metal ions having a valency selected from the group consisting of +2 and +3; and ii. a plurality of organic ligands, the plurality of organic ligands comprising a) an organic ligand derived from a compound of Formula I;b) one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III, preferably the or each further organic ligand is derived from a compound of Formula II; andc) optionally, an organic ligand derived from the group consisting of 1H- 1,2,4-triazole, 2H-l,2,3-trizaole, lH-l,2,3-triazole, and combinations thereof; wherein each R1is independently selected from the group consisting of -CF3, CHF2, R4, NH2, substituted amino, Cl, Br, I, NO2, C(O)R4, OH, aryl, substituted aryl; wherein each R2and each R3is independently selected from the group consisting of Br, Cl, I, F, CF3, CHF2, NH2, substituted amino, NO2, R4, CO2R4, CO2H, CONH2, SH, and CN; wherein R4is Ci to C4 alkyl or substituted Ci to C4 alkyl; wherein m = 0, 1 or 2 wherein n = 1 or 2; and wherein p = 1 or 2.

[0008] Optionally, the MOF may consist essentially of, or consist of, a plurality of metal ions and a plurality of organic ligands as described herein.

[0009] Each metal ion of the plurality of metal ions may be the ion of a metal independently selected from the group consisting of zinc, aluminium, indium, scandium, gallium, vanadium, zirconium, iron, copper, cobalt, magnesium, chromium, nickel, and manganese . Preferably, each metal ion is an ion of zinc or aluminium. More preferably, each metal ion is a zinc ion.

[0010] Alternatively or additionally, the plurality of metal ions may (as a plurality) consist essentially of (that is to say substantially all of the metal ions within the MOF are the same), or consist of, ions of a metal selected from the group consisting of: zinc, aluminium, indium,scandium, gallium, vanadium, zirconium, iron, copper, cobalt, magnesium, chromium, nickel, and manganese, more preferably the plurality of metal ions may consist essentially of ions, or consist of ions, of a metal selected from the group consisting of: zinc and aluminium; most preferably the plurality of metal ions may consist essentially of ions, or consist of ions, of zinc.

[0011] In the compound of Formula I, the CO2H may be at the 4-position, the 3-position or the 5-position. Preferably, the CO2H is at the 4-position.

[0012] Optionally, m is 0. Preferably, m is 0 and the CO2H is at the 4-position. Alternatively, m is 0 and the CO2H is at the 3-position or m is 0 and the CO2H is at the 5-position.

[0013] Optionally, m is 1. When m is 1, R1may be selected from the group consisting of halogens (such as Cl, Br, F or I), R4, CF3, CHF2, NH2, NO2, C(O)R4, OH, aryl, and substituted aryl, Preferably, R1is selected from the group consisting of 5-CI, 4-CI, 3-CI, 5-Br, 4-Br, 3-Br, 4-1, 5- CH3, 3-CH3, 5-CH(CH3)2, 3-CH2CH2CH3, 3-C(CH3)3, 5-CF3, 4-CF3, 3-CF3, 5-CHF2, 5-NH2, 4-NH2, 3- NH2, 5-NO2, 4-NO2, 3-NO2, 5-C(O)CH3, 5-OH, 5-(4-methoxyphenyl), 5-phenyl, 5-(4- nitrophenyl), 5-(4-fluorophenyl), 5-(3-nitrophenyl), 5-(2-methoxyphenyl), 5-(2,5- dimethoxyphenyl), 5-(3-chlorophenyl), 5-(furan-2-yl), 3-hydroxymethyl, 3-phenyl, 3-(4- hydroxyphenyl), 3-(2-fluorophenyl), and 3-(3-methoxyphenyl).

[0014] Optionally, m is 2. When m is 2, each R1is independently selected from the group consisting of R4, halogens (such as Br, CL, I, F), NH2, NO2, CF3, or both R1are linked to form a fused cycloalkane or a fused heterocycle. Preferably, when m is 2, (i) one R1is 3-CH3and one R1is 5-CH3, (ii) one R1is 4-Br and one R is 5-CH3, (Hi) one R1is 3-NH2 and one R1is 4-Br, (iv) one R1is 3-Br and one R1is 4-CH3, (v) one R1is 4-NH2 and one R1is 3-CH3, (vi) one R1is 4-NO2 and one R1is 3-CF3, or (vii) both R1are CH3 (viii) both R1are linked to form a fused cycloalkane, preferably l,4,5,6-tetrahydrocyclopentane[c]pyrazole-3-carboxylic acid, or (ix) both R1are linked to form a fused heterocycle, preferably l,4,6,7-tetrahydropyrano[4,3-c]pyrazole-3- carboxylic acid

[0015] When, in Formula I, the CO2H is at the 4-position, preferably (i) m = 0; (ii) m = 1 and R1is selected from the group consisting of 5-CF3, 3-NH2, 5-CH3, 5-CHF2, 5-CI, 3-CH3, and 3-CI; or (iii) m = 2 and one R1is 3-CH3 and one R1is 5-CH3.

[0016] When, in Formula I, the CO2H is at the 3-position, preferably (i) m = 0; (ii) m = 1 and R1is selected from the group consisting of 4-NH2, 4-Br, 4-NO2, 4-CF3, 5-CI, 5-CH3, 5-CH(CH3)2, 5- NH2, 5-Br, 5-C(O)CH3, 5-OH, 5-(4-methoxyphenyl), 5-CHF2, 5-CF3, 5-phenyl, 5-(4-nitrophenyl), 5-(4-fluorophenyl), 5-(3-nitrophenyl), 5-(2-methoxyphenyl), 5-(2,5-dimethoxyphenyl), 5-(3- chlorophenyl), and 5-(furan-2-yl); or (iii) m = 2 and wherein (a) one R1is 4-Br and one R is 5- CH3, (b) both R1are linked to form a fused cycloalkane, preferably 1, 4,5,6- tetrahydrocyclopentane[c]pyrazole-3-carboxylic acid, or (c) both R1are linked to form a fused heterocycle, preferably l,4,6,7-tetrahydropyrano[4,3-c]pyrazole-3-carboxylic acid.

[0017] When, in Formula I, the CO2H is at the 5-position, preferably (i) m = 0; (ii) m = 1 and R1is selected from the group consisting of 4-1, 4-CI, 3-Br, 3-CH2CH2CH3, 3-NO2, 3-CH3, 3- hydroxymethyl, 4-Br, 3-C(CH3)3, 3-phenyl, 3-(4-hydroxyphenyl), 3-(2-fluorophenyl), and 3-(3- methoxyphenyl); or (iii) m = 2 and wherein (a) one R1is 3-NH2 and one R1is 4-Br, (b) one R1is 3-Br and one R1is 4-CH3, (c) one R1is 4-NH2 and one R1is 3-CH3, (d) one R1is 4-NO2 and one R1is 3-CF3, or (e) both R1are CH3.

[0018] Preferred compounds of Formula I include the group consisting of lH-pyrazole-4- carboxylic acid, 3-Amino-lH-pyrazole-4-carboxylic acid, 5-Amino-lH-pyrazole-4-carboxylic acid, 5-(Difluoromethyl)-lH-pyrazole-4-carboxylic acid, 5-(trifluoromethyl)-lH-pyrazole-4- carboxylic acid, 3-(Difluoromethyl)-lH-pyrazole-4-carboxylic acid, 3-(trifluoromethyl)-lH- pyrazole-4-carboxylic acid, 5-Chloro-lH-pyrazole-4-carboxylic acid, 5-Methyl-lH-pyrazole-4- carboxylic acid, 3-Methyl-lH-pyrazole-4-carboxylic acid, 3-Chloro-lH-pyrazole-4-carboxylic acid, lH-Pyrazole-3-carboxylic acid, 4-Amino-lH-pyrazole-3-carboxylic acid, 5-Amino-lH- pyrazole-3-carboxylic acid, 4-Bromo-lH-pyrazole-3-carboxylic acid, 4-Nitro-lH-pyrazole-3- carboxylic acid, 4-(Trifluoromethyl)-lH-pyrazole-3-carboxylic acid, 5-Chloro-lH-pyrazole-3- carboxylic acid, 5-Methyl-lH-pyrazole-3-carboxylic acid, 5-lsopropyl-lH-pyrazole-3-carboxylic acid, 5-Amino-lH-pyrazole-3-carboxylic acid, 4-Bromo-5-methyl-lH-pyrazole-3-carboxylic acid, 5-Bromo-lH-pyrazole-3-carboxylic acid, 5-Acetyl-lH-pyrazole-3-carboxylic acid, 5- Hydroxy-lH-pyrazole-3-carboxylic acid, 5-(4-Methoxyphenyl)-lH-pyrazole-3-carboxylic acid, 5-(Difluoromethyl)-lH-pyrazole-3-carboxylic acid, 5-(Trifluoromethyl)-lH-pyrazole-3- carboxylic acid, 4-(Difluoromethyl)-lH-pyrazole-3-carboxylic acid, 4-(Trifluoromethyl)-lH-pyrazole-3-carboxylic acid, l,4,5,6-Tetrahydrocyclopenta[c]pyrazole-3-carboxylic acid, 5- Hydroxy-lH-pyrazole-3-carboxylic acid, lH-pyrazole-5-carboxylic acid, 4-lodo-lH-pyrazole-5- carboxylic acid, 4-Chloro-lH-pyrazole-5-carboxylic acid, 4-amino-lH-pyrazole-5-carboxylic acid, 3-amino-lH-pyrazole-5-carboxylic acid, 3-Bromo-lH-pyrazole-5-carboxylic acid, 3- Propyl-lH-pyrazole-5-carboxylic acid, 3-Nitro-lH-pyrazole-5-carboxylic acid, 3-Methyl-lH- pyrazole-5-carboxylic acid, 3-Amino-4-bromo-lH-pyrazole-5-carboxylic acid, 3-Bromo-4- methyl-lH-pyrazole-5-carboxylic acid, 4-Amino-3-methyl-lH-pyrazole-5-carboxylic acid, 4- Nitro-3-(trifluoromethyl)-lH-pyrazole-5-carboxylic acid, 3-(Hydroxymethyl)-lH-pyrazole-5- carboxylic acid, 3,4-Dimethyl-lH-pyrazole-5-carboxylic acid, 4-Bromo-lH-pyrazole-5- carboxylic acid, 3-(tert-Butyl)-lH-pyrazole-5-carboxylic acid, 3-(Difluoromethyl)-lH-pyrazole- 5-carboxylic acid, 3-(Trifluoromethyl)-lH-pyrazole-5-carboxylic acid, 4-(Difluoromethyl)-lH- pyrazole-5-carboxylic acid, and 4-(Trifluoromethyl)-lH-pyrazole-5-carboxylic acid 3-Phenyl- lH-pyrazole-5-carboxylic acid, 5-Phenyl-lH-pyrazole-3-carboxylic acid, 3-(4-Hydroxyphenyl)- lH-pyrazole-5-carboxylic acid, 5-(4-Nitrophenyl)-lH-pyrazole-3-carboxylic acid, 5-(4- Fluorophenyl)-lH-pyrazole-3-carboxylic acid, 5-(3-Nitrophenyl)-lH-pyrazole-3-carboxylic acid, 5-(2-Methoxyphenyl)-lH-pyrazole-3-carboxylic acid, 5-Amino-lH-pyrazole-3-acetic acid, l,4,6,7-Tetrahydropyrano[4,3-c]pyrazole-3-carboxylic acid, 5-(2,5-Dimethoxyphenyl)-lH- pyrazole-3-carboxylic acid, 5-(3-Chlorophenyl)-lH-pyrazole-3-carboxylic acid, 3-(2- Fluorophenyl)-lH-pyrazole-5-carboxylic acid, 3-(3-Methoxyphenyl)-lH-pyrazole-5-carboxylic acid, and 5-(Furan-2-yl)-lH-pyrazole-3-carboxylic acid.

[0019] Particularly preferred compounds of Formula I include the group consisting of 1H- pyrazole-4-carboxylic acid, 3-Amino-lH-pyrazole-4-carboxylic acid, 5-Amino-lH-pyrazole-4- carboxylic acid, 5-(Difluoromethyl)-lH-pyrazole-4-carboxylic acid, 5-(trifluoromethyl)-lH- pyrazole-4-carboxylic acid, 3-(Difluoromethyl)-lH-pyrazole-4-carboxylic acid, 3- (trifluoromethyl)-lH-pyrazole-4-carboxylic acid, 5-Chloro-lH-pyrazole-4-carboxylic acid, 5- Methyl-lH-pyrazole-4-carboxylic acid, 3-Methyl-lH-pyrazole-4-carboxylic acid, 3-Chloro-lH- pyrazole-4-carboxylic acid, lH-Pyrazole-3-carboxylic acid, 4-Amino-lH-pyrazole-3-carboxylic acid, 5-Amino-lH-pyrazole-3-carboxylic acid, 4-Bromo-lH-pyrazole-3-carboxylic acid, 4-Nitro- lH-pyrazole-3-carboxylic acid, 4-(Trifluoromethyl)-lH-pyrazole-3-carboxylic acid, 5-Chloro- lH-pyrazole-3-carboxylic acid, 5-Methyl-lH-pyrazole-3-carboxylic acid, 5-lsopropyl-lH- pyrazole-3-carboxylic acid, 5-Amino-lH-pyrazole-3-carboxylic acid, 4-Bromo-5-methyl-lH-pyrazole-3-carboxylic acid, 5-Bromo-lH-pyrazole-3-carboxylic acid, 5-Acetyl-lH-pyrazole-3- carboxylic acid, 5-Hydroxy-lH-pyrazole-3-carboxylic acid, 5-(4-Methoxyphenyl)-lH-pyrazole- 3-carboxylic acid, 5-(Difluoromethyl)-lH-pyrazole-3-carboxylic acid, 5-(Trifluoromethyl)-lH- pyrazole-3-carboxylic acid, 4-(Difluoromethyl)-lH-pyrazole-3-carboxylic acid, 4- (Trifluoromethyl)-lH-pyrazole-3-carboxylic acid, l,4,5,6-Tetrahydrocyclopenta[c]pyrazole-3- carboxylic acid, 5-Hydroxy-lH-pyrazole-3-carboxylic acid, lH-pyrazole-5-carboxylic acid, 4- lodo-lH-pyrazole-5-carboxylic acid, 4-Chloro-lH-pyrazole-5-carboxylic acid, 4-amino-lH- pyrazole-5-carboxylic acid, 3-amino-lH-pyrazole-5-carboxylic acid, 3-Bromo-lH-pyrazole-5- carboxylic acid, 3-Propyl-lH-pyrazole-5-carboxylic acid, 3-Nitro-lH-pyrazole-5-carboxylic acid, 3-Methyl-lH-pyrazole-5-carboxylic acid, 3-Amino-4-bromo-lH-pyrazole-5-carboxylic acid, 3- Bromo-4-methyl-lH-pyrazole-5-carboxylic acid, 4-Amino-3-methyl-lH-pyrazole-5-carboxylic acid, 4-Nitro-3-(trifluoromethyl)-lH-pyrazole-5-carboxylic acid, 3-(Hydroxymethyl)-lH- pyrazole-5-carboxylic acid, 3,4-Dimethyl-lH-pyrazole-5-carboxylic acid, 4-Bromo-lH-pyrazole- 5-carboxylic acid, 3-(tert-Butyl)-lH-pyrazole-5-carboxylic acid, 3-(Difluoromethyl)-lH- pyrazole-5-carboxylic acid, 3-(Trifluoromethyl)-lH-pyrazole-5-carboxylic acid, 4- (Difluoromethyl)-lH-pyrazole-5-carboxylic acid, and 4-(Trifluoromethyl)-lH-pyrazole-5- carboxylic acid. More preferred compounds of Formula I include the group consisting of 1H- pyrazole-4-carboxylic acid, lH-pyrazole-3-carboxylic acid, lH-pyrazole-5-carboxylic acid, 3- Amino-lH-pyrazole-4-carboxylic acid, 5-Amino-lH-pyrazole-4-carboxylic acid, 5- (Difluoromethyl)-lH-pyrazole-4-carboxylic acid, 5-(trifluoromethyl)-lH-pyrazole-4-carboxylic acid, 3-(Difluoromethyl)-lH-pyrazole-4-carboxylic acid, 3-(trifluoromethyl)-lH-pyrazole-4- carboxylic acid, 5-(Difluoromethyl)-lH-pyrazole-3-carboxylic acid, 5-(Trifluoromethyl)-lH- pyrazole-3-carboxylic acid, 4-(Difluoromethyl)-lH-pyrazole-3-carboxylic acid, 4- (Trifluoromethyl)-lH-pyrazole-3-carboxylic acid, 4-Amino-lH-pyrazole-3-carboxylic acid, 5- Amino-lH-pyrazole-3-carboxylic acid, 4-amino-lH-pyrazole-5-carboxylic acid, 3-amino-lH- pyrazole-5-carboxylic acid, 3-(Difluoromethyl)-lH-pyrazole-5-carboxylic acid, 3- (Trifluoromethyl)-lH-pyrazole-5-carboxylic acid, 4-(Difluoromethyl)-lH-pyrazole-5-carboxylic acid, and 4-(Trifluoromethyl)-lH-pyrazole-5-carboxylic acid. Most preferred compounds of Formula I include the group consisting of lH-pyrazole-4-carboxylic acid, lH-pyrazole-3- carboxylic acid, and lH-pyrazole-5-carboxylic acid.

[0020] In some embodiments, the MOF may comprise substantially only one species of organic ligand derived from Formula I, preferably the MOF comprises only one species of organic ligand derived from Formula I.

[0021] The MOF may comprise one or more species of organic ligand derived from a compound of Formula I. The MOF may comprise two or more species of organic ligand derived from a compound of Formula I. In said embodiment, the two or more species of organic ligand derived from a compound of Formula I differ from one another. For example, the MOF may comprise two species of organic ligand derived from a compound of Formula I, e.g. an organic ligand derived from a first compound of Formula I and an organic ligand derived from a second (different) compound of Formula I. Alternatively, the MOF may comprise three species of organic ligand derived from a compound of Formula I, e.g. each of the three organic ligands derived from a compound of Formula I may be different.

[0022] Typically, the MOF comprises organic ligand derived from a compound of Formula II. The MOF may comprise one or more species of organic ligand derived from a compound of Formula II, for example, two or more, or three or more, such as two or three. Preferably, the MOF comprises one species of organic ligand derived from a compound of Formula II. Alternatively, the MOF comprises two species of organic ligand derived from a compound of Formula II.

[0023] Alternatively or additionally, the MOF may comprise organic ligand derived from a compound of Formula III. The MOF may comprise one or more species of organic ligand derived from a compound of Formula III, for example, two or more, or three or more, such as two or three. The MOF may comprise one species of organic ligand derived from a compound of Formula III or the MOF may comprise two species of organic ligand derived from a compound of Formula III.

[0024] In embodiments, when the MOF comprises ligand derived from a compound of Formula II, the MOF comprises only organic ligand derived from a single compound of Formula II (i.e. substantially only one species of organic ligand derived from Formula II is present in the MOF) and / or when the MOF comprises ligand derived from a compound of Formula III, theMOF comprises only organic ligand derived from a single compound of Formula III (i.e. substantially only one species of organic ligand derived from Formula III is present in the MOF). Additionally, or alternatively, the MOF may comprise substantially only one species of organic ligand derived from Formula I.

[0025] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I and b) organic ligand derived from a single compound of Formula II (i.e. substantially only one species of organic ligand derived from each of Formula I and Formula II is present in the MOF).

[0026] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I and b) organic ligand derived from two compounds of Formula II (i.e. substantially only one species of organic ligand derived from Formula I and substantially only two species of organic ligand derived from Formula II is present in the MOF).

[0027] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I, b) organic ligand derived from a single compound of Formula II and c) organic ligand derived from a single compound of Formula III (i.e. substantially only one species of organic ligand derived from each of Formula I, Formula II and Formula III is present in the MOF).

[0028] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I and b) organic ligand derived from a single compound of Formula III (i.e. substantially only one species of organic ligand derived from each of Formula I and Formula III is present in the MOF).

[0029] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I and b) organic ligand derived from two compounds of Formula III (i.e. substantiallyonly one species of organic ligand derived from Formula I and substantially only two species of organic ligand derived from Formula III is present in the MOF).

[0030] Preferably, the metal organic framework comprises organic ligand derived from a compound of Formula II. Optionally, n = 1. When n = 1, R2may be selected from the group consisting of halogens (such as Cl, Br, I or F), NH2, substituted amino, CO2H, CN, CONH2, CO2R4, R4, SH, NO2, CHF2, and CF3. For example, R2may be selected from the group consisting of 3-CI, 3-1, 3-Br, 5-Br, 3-NH2, 5-NH2, 3-CO2H, 3-CN, 3-C(O)NH2, 3-CO2CH3, 5-CO2CH2CH3, 3-CH3, 5-CH3, 3-CH2CH3, 5-CH2CH3, 3-CHF2, 5-CHF2, 3- CF3, 5-CF3, 3-SH, 3-NO2and 5-NO2.

[0031] Alternatively or additionally, for example, n may be 2. In this embodiment, the two R2groups may be as follows: (i) one R2is 3-NH2 and one R2is 5-NH2, (ii) one R2is 3-CI and one R2is 5-CI, (iii) one R2is 3-Br and one R2is 5-Br, (iv) one R2is 3-CH3and one R2is 5-CH3, (v) one R2is 3-CN and one R2is 5-NH2, (vi) one R2is 3-CO2CH3and one R2is 5-NH2, (vii) one R2is 3-SH and one R2is 5-CH3, (viii) one R2is 3-NH2 and one R2is 5-SH, (ix) one R2is 3-CO2CH3and one R2is 5-Br, (x) one R2is 3-CO2H and one R2is 5-Br, (xi) one R2is 3-CO2CH2CH3and one R2is 5-CI, (xii) one R2is 3-SH and one R2is 5-CF3, (xiii) one R2is 3-CO2H and one R2is 5-N H2, or (xiv) one R2is 3-NH2 and one R2is 5-CO2H.

[0032] Preferably, the metal organic framework comprises organic ligand derived from a compound of Formula III. Optionally, p = 1. When p = 1, R3may be selected from the group consisting of halogens (such as Cl, Br, I or F), CO2H, CONH2, CO2R4,R4, SH, NO2, NH2, substituted amino, CN, CHF2, and CF3. For example, R3may be selected from the group consisting of 4-Br, 5-Br, 4-NO2, 5-NO2, 4-NH2, 5-NH2, 4-CH3, 4-CO2CH2CH3, 4-CO2CH3, and 4-CO2H.

[0033] Additionally or alternatively, the metal organic framework may comprise organic ligand derived from a compound of Formula III, wherein p = 2. In this embodiment, one R3may be 4-Br and one R3may be 5-Br.

[0034] The substituted amino group herein may be for example NHR, NR2, NHC(O)R, wherein each R may be independently selected from the group consisting of alkyl (such as Ci to C4 alkyl), substituted alkyl (such as substituted Ci to C4 alkyl), alkenyl (such as Ci to C4 alkenyl),substituted alkenyl (such as substituted Ci to C4 alkenyl), aryl, and substituted aryl. The substituent in the substituted amino group may be introduced by post-synthetic functionalisation. Such functionalisation reactions are well within the common general knowledge of the skilled person.

[0035] Preferred compounds of Formula II include the group consisting of 3-methyl-lH-l,2,4- triazole, 3-amino-lH-l,2,4-triazole, 3-Chloro-l,2,4-triazole, l,2,4-Triazole-3-carboxylic acid, 3,5-Diamino-l,2,4-triazole, 3-lodo-lH-l,2,4-triazole, 3-Bromo-4H-l,2,4-triazole, 2H-1,2,4- Triazole-3-carboxamide, 5-Bromo-lH-l,2,4-triazole, 3-Methyl-lH-l,2,4-triazole, 1H-1,2,4- Triazole-3-thiol, 3-Nitro-lH-l,2,4-triazole, 3-Ethyl-lH-l,2,4-triazole, 3,5-Dichloro-lH-l,2,4- triazole, 3,5-Dibromo-lH-l,2,4-triazole, Methyl lH-l,2,4-triazole-3-carboxylate, 3- (Trifluoromethyl)-lH-l,2,4-triazole, 3,5-Dimethyl-4H-l,2,4-triazole, Ethyl lH-l,2,4-triazole-5- carboxylate, 5-Amino-lH-l,2,4-triazole-3-carbonitrile, Methyl 5-Amino-l,2,4-triazole-3- carboxylate, 5-Methyl-l,2-dihydro-3H-l,2,4-triazole-3-thione, 3-Amino-lH-l,2,4-triazole-5- thiol, Methyl 5-bromo-lH-l,2,4-triazole-3-carboxylate, 5-Bromo-lH-l,2,4-triazole-3- carboxylic acid, Ethyl 5-chloro-lH-l,2,4-triazole-3-carboxylate, 5-(Trifluoromethyl)-4H-l,2,4- triazole-3-thiol, 5-Amino-4H-l,2,4-triazole-3-carboxylic acid, 3-Amino-lH-l,2,4-triazole-5- carboxylic acid hydrate, and combinations thereof.

[0036] Particularly preferred compounds of Formula II include the group consisting of 3- methyl-lH-l,2,4-triazole, 3-amino-lH-l,2,4-triazole, 3-Ch loro-1, 2, 4-triazole, l,2,4-Triazole-3- carboxylic acid, 3, 5-Diamino-l, 2, 4-triazole, 3-lodo-lH-l, 2, 4-triazole, 3-Bromo-4H-l,2,4- triazole, 2H-l,2,4-Triazole-3-carboxamide, 5-Bromo-lH-l, 2, 4-triazole, 3-Methyl-lH-l,2,4- triazole, lH-l,2,4-Triazole-3-thiol, 3-Nitro-lH-l, 2, 4-triazole, 3-Ethyl-lH-l, 2, 4-triazole, 3,5- Dichloro-1H-1, 2, 4-triazole, 3, 5-Dibromo-lH-l, 2, 4-triazole, Methyl lH-l,2,4-triazole-3- carboxylate, 3-(Trifluoromethyl)-lH-l, 2, 4-triazole, 3, 5-Dimethyl-4H-l, 2, 4-triazole, and combinations thereof. Most preferred compounds of Formula II include the group consisting of 3-methyl-lH-l, 2, 4-triazole, 3-amino-lH-l, 2, 4-triazole, and combinations thereof.

[0037] Preferred compounds of Formula III include the group consisting of 4-Bromo-2H-l,2,3- triazole, 4-Nitro-2H-l,2,3-triazole, 4-Methyl-lH-l,2,3-triazole, 5-Bromo-lH-l,2,3-triazole, 4- Methyl-2H-l,2,3-triazole, 4,5-Dibromo-2H-l,2,3-triazole, Ethyl 2H-l,2,3-triazole-4-carboxylate, 4,5-Dibromo-lH-l,2,3-triazole, Methyl lH-l,2,3-triazole-4-carboxylate, 1H- [l,2,3]Triazole-4-carboxylic acid, and combinations thereof.

[0038] Particularly preferred compounds of Formula III include the group consisting of 4- Bromo-2H-l,2,3-triazole, 4-Nitro-2H-l,2,3-triazole, 4-Methyl-lH-l,2,3-triazole, 5-Bromo-lH- 1,2,3-triazole, 4-Methyl-2H-l,2,3-triazole, 4,5-Dibromo-2H-l,2,3-triazole, and combinations thereof.

[0039] Preferably, m = 0 and the CO2H is at the 4-position. Preferably, the or each further organic ligand is derived from a compound of Formula II, wherein n = 1 and R2is independently selected from the groups consisting of R4and NH2. Preferably, the MOF comprises 1,2,4- triazole.

[0040] Preferred MOFs include those comprising (i) zinc ion, organic ligand derived from 1H- pyrazole-4-carboxylic acid and organic ligand derived from 3-methyl-lH-l,2,4-triazole; (ii) zinc ion, organic ligand derived from lH-pyrazole-4-carboxylic acid and organic ligand derived from 3-amino-lH-l,2,4-triazole; (iii) zinc ion, organic ligand derived from lH-pyrazole-4-carboxylic acid, organic ligand derived from 3-methyl-lH-l,2,4-triazole, organic ligand derived from 3- amino-lH-l,2,4-triazole and organic ligand derived from 1,2,4-triazole; (iv) zinc ion, organic ligand derived from lH-pyrazole-4-carboxylic acid and organic ligand derived from 5-methyl- lH-l,2,4-triazole; (v) zinc ion, organic ligand derived from lH-pyrazole-4-carboxylic acid and organic ligand derived from 3-amino-lH-l,2,4-triazole; (vi) zinc ion, organic ligand derived from lH-pyrazole-4-carboxylic acid, organic ligand derived from 5-methyl-lH-l,2,4-triazole, organic ligand derived from 5-amino-lH-l,2,4-triazole and organic ligand derived from 1,2,4- triazole, (vii) zinc ion, organic ligand derived from lH-pyrazole-4-carboxylic acid, organic ligand derived from 3-methyl-lH-l,2,4-triazole, organic ligand derived from 5-amino-lH-l,2,4- triazole and organic ligand derived from 1,2,4-triazole; and (viii) zinc ion, organic ligand derived from lH-pyrazole-4-carboxylic acid, organic ligand derived from 5-methyl-lH-l,2,4- triazole, organic ligand derived from 3-amino-lH-l,2,4-triazole and 1,2,4-triazole.

[0041] When the organic ligands comprise, for example a Ci to C4 alkyl group, such as in 3- methyl-lH-l,2,4-triazole, the hydrophobicity of the MOF may be enhanced.

[0042] Preferably, the MOF comprises an organic ligand derived from the group consisting of lH-l,2,4-triazole, 2H-l,2,3-trizaole, lH-l,2,3-triazole, and combinations thereof, more preferably the MOF comprises an organic ligand derived from lH-l,2,4-triazole.

[0043] Optionally, the plurality of organic ligands may comprise oxalic acid. The MOF may comprise oxalic acid.

[0044] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I, b) organic ligand derived from a single compound of Formula II (i.e. substantially only one species of organic ligand derived from each of Formula I and Formula II is present in the MOF), and c) organic ligand derived from oxalic acid.

[0045] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I, b) organic ligand derived from two compounds of Formula II (i.e. substantially only one species of organic ligand derived from Formula I and substantially only two species of organic ligand derived from Formula II is present in the MOF) , and c) organic ligand derived from oxalic acid.

[0046] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I, b) organic ligand derived from a single compound of Formula II, c) organic ligand derived from a single compound of Formula III (i.e. substantially only one species of organic ligand derived from each of Formula I, Formula II and Formula III is present in the MOF), and d) organic ligand derived from oxalic acid.

[0047] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I, b) organic ligand derived from a single compound of Formula III (i.e. substantiallyonly one species of organic ligand derived from each of Formula I and Formula III is present in the MOF), and c) organic ligand derived from oxalic acid.

[0048] In embodiments, the MOF may comprise a mixture of organic ligand, the mixture consisting of or consisting essentially of a) organic ligand derived from a single compound of Formula I, b) organic ligand derived from two compounds of Formula III (i.e. substantially only one species of organic ligand derived from Formula I and substantially only two species of organic ligand derived from Formula III is present in the MOF), and c) organic ligand derived from oxalic acid.

[0049] The metal organic framework may comprise organic ligand derived from compound of Formula I and further organic ligand derived from compound of Formula II and / or compound of Formula III in a molar ratio of from about 1:19 to about 19:1. Preferably, the metal organic framework may comprise organic ligand derived from compound of Formula I and further organic ligand derived from compound of Formula II and / or compound of Formula III, in a molar ratio of from about 1:10 to 10:1, preferably from about 1:4 to about 4:1, preferably from about 1:2 to about 2:1.

[0050] When the MOF comprises one species of organic ligand derived from compound of Formula I and one species of further organic ligand derived from compound of Formula II or a compound of Formula III, the metal organic framework may comprise organic ligand derived from compound of Formula I and further organic ligand in a molar ratio of from about 1:19 to about 19:1, preferably in a molar ratio of from about 1:10 to 10:1, preferably from about 1:4 to about 4:1, preferably from about 1:1 to about 2:1.

[0051] The metal organic framework may comprise metal ion and organic ligand derived from compound of Formula I in a molar ratio of about from 40:1 to about 1:2, preferably from about 2:1 to about 1:1. When the MOF comprises one species of metal ion and one species of organic ligand derived from compound of Formula I, the metal organic framework may comprise metal ion and organic ligand derived from compound of Formula I in a molar ratio of about from 40:1 to about 1:2, preferably from about 2:1 to about 1:1.

[0052] The metal organic framework may comprise metal ion and further organic ligand derived from compound of Formula II or compound of Formula III in a molar ratio of from about 40:1 to about 1:2, preferably from about 2:1 to about 1:1. When the MOF comprises one species of metal ion and one species of further organic ligand derived from compound of Formula II or compound of Formula III, the MOF comprises metal ion and further organic ligand in a molar ratio of about from 40:1 to about 1:2, preferably from about 2:1 to about 1:1.

[0053] When the metal organic framework comprises organic ligand derived from compound of Formula II and organic ligand derived from compound of Formula III, the metal organic framework may comprise organic ligand derived from compound of Formula II and organic ligand derived from compound of Formula III in a molar ratio of from about 10:1 to about 1:10. When the MOF comprises one species of organic ligand derived from compound of Formula II and one species of organic ligand derived from compound of Formula III, the metal organic framework may comprise organic ligand derived from compound of Formula II and organic ligand derived from compound of Formula III in a molar ratio of from about 10:1 to about 1:10.

[0054] When the plurality of organic ligands comprises two species of further organic ligand derived from compound of Formula II, the plurality of organic ligands may comprise first species of further organic ligand derived from compound of Formula II and second species of further organic ligand derived from compound of Formula II in a molar ratio of from about 1:19 to about 19:1, preferably in a molar ratio of from about 1:10 to 10:1, preferably from about 1:4 to about 4:1, from about 1:2 to about 2:1. Typically, the plurality of organic ligands comprise substantially only two species of further organic ligand derived from compound of Formula II.

[0055] When the plurality of organic ligands comprises oxalic acid, the MOF may comprise organic ligand derived from compound of Formula I and organic ligand derived from oxalic acid in a molar ratio of from about 1:1 to about 9:1.

[0056] Preferably, the metal organic framework comprises (a) from about 20% to about 50%, preferably from about 30% to about 40%, metal ion by weight of the metal organic framework, (b) from about 10% to about 50%, preferably from about 10% to about 40%, preferably fromabout 20% to about 30%, organic ligand derived from compound of Formula I by weight of the metal organic framework, and (c) from about 10% to about 50%, preferably from about 20% to about 40%, further organic ligand derived from compound of Formula II and / or compound of Formula III.

[0057] When the MOF comprises one species of metal ion, one species of organic ligand derived from compound of Formula I and one species of further organic ligand derived from compound of Formula II or compound of Formula III, the metal organic framework may comprise (a) from about 20% to about 50%, preferably from about 30% to about 40%, metal ion by weight of the metal organic framework, (b) from about 10% to about 50%, preferably from about 10% to about 40%, preferably from about 20% to about 30%, organic ligand derived from compound of Formula I by weight of the metal organic framework, and (c) from about 10% to about 50%, preferably from about 20% to about 40%, further organic ligand.

[0058] Preferably, the metal organic framework has a BET area, as measured by N2 adsorption at 77 K, of from about 500 m2 / g to about 1500 m2 / g, preferably from about 600 m2 / g to about 1200 m2 / g, preferably from about 700 m2 / g to about 1100 m2 / g, preferably from about 750 m2 / g to about 1000 m2 / g, preferably from about 800 m2 / g to about 925 m2 / g, preferably from about 850 to about 900 m2 / g. Preferably, the metal organic framework has a BET area, as measured by N2 adsorption at 77 K, of from about 750 m2 / g to about 850 m2 / g.

[0059] Preferably, the metal-organic framework has a micropore volume of from about 0.15 cm3 / g to about 0.5 cm3 / g as measured using nitrogen adsorption at 77K.

[0060] The metal organic framework may be in the form of a powder. MOF powder particles typically comprise MOF crystallites that may have been aggregated together during a solvent removal process. Alternatively, the metal organic framework may be in the form of MOF crystallites / particles, optionally MOF crystal lites / pa rticles dispersed in a slurry with solvent. Such slurries can include the reaction mixes used in the synthesis of the MOFs as described herein.

[0061] The MOF may have a CO2 adsorption capacity of from about 1.0 mmol / g to about 3 mmol / g, preferably from about 1.5 mmol / g to about 2.5 mmol / g, preferably from about 1.7 mmol to about 2.5 mmol / g, preferably from about 2.0 mmol / g to about 2.3 mmol / g at 21 °C (room temperature herein) at 0.15 bar (15 kPa). The CO2 adsorption capacity is measured by the method described herein.

[0062] The MOF may have a CO2 adsorption capacity of from about 2.5 mmol / g to about 5.0 mmol / g, preferably from about 3.0 mmol / g to about 4.5 mmol / g, preferably from about 3.5 mmol to about 4.25 mmol / g, preferably from about 4.0 mmol / g to about 4.1 mmol / g at 21 °C at 1 bar (100 kPa). The CO2 adsorption capacity is measured by the method described herein.

[0063] MOFs according to the first aspect of the invention may be particularly advantageous as they may display strong CO2 interactions meaning relatively good CO2 adsorption capacity and relatively low water adsorption. Without wishing to be bound by theory, these properties combine to provide a MOF that is stable and suitable for humid air and / or high temperature (e.g. in industrial emissions) high concentration carbon dioxide capture applications, also in combination with binders. MOFs of the invention are suitable for use under a range of conditions. For example, systems that capture CO2 directly from the atmosphere to capturing CO2 from the flue gases of thermal power plants and cement works and the like. The skilled person will appreciate that MOFs that are optimised for one application, such as direct air capture, may not be most appropriate for other applications.

[0064] The Inventors have found that the MOFs of the first aspect, and mixtures of such MOFs and binders, are relatively stable at elevated temperatures and / or high humidities, which makes them especially suitable for some flue gas applications and swing adsorption processes (pressure or temperature, for example), especially when steam is used to regenerate the sorbent. In addition, the selectivity of the MOFs for CO2 allows capture of CO2 in the presence of contaminants that may be present in flue gases. Without wishing to be bound by theory, it is believed that the use of organic ligands comprising an aromatic ring increases the proportion of non-polar regions in the ligand meaning that the chances of coordination of water to the MOF are relatively low. The advantages of the MOFs of the first aspect of the invention are demonstrated in the Examples and Figures described herein.

[0065] In a related aspect, the invention provides a metal organic framework (MOF) comprising i. a plurality of metal ions, the plurality of metal ions consisting of ions of a metal selected from the group consisting of: zirconium, zinc and aluminium; and ii. a plurality of organic ligands, the plurality of organic ligands comprising a) an organic ligand derived from a compound of Formula I;b) one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III, preferably the or each further organic ligand is derived from a compound of Formula II; andc) optionally, an organic ligand derived from the group consisting of 1H- 1,2,4-triazole, 2H-l,2,3-trizaole, lH-l,2,3-triazole, and combinations thereof; wherein each R1is independently selected from the group consisting of -CF3, CHF2, R4, NH2, substituted amino, Cl, Br, I, NO2, C(O)R4, OH, aryl, substituted aryl; wherein each R2and each R3is independently selected from the group consisting of Br, Cl, I, F, CF3, CHF2, NH2, substituted amino, NO2, R4, CO2R4, CO2H, CONH2, SH, and CN; wherein R4is Ci to C4 alkyl or substituted Ci to C4 alkyl; wherein m = 0, 1 or 2 wherein n = 1 or 2; andwherein p = 1 or 2.

[0066] For the avoidance of doubt, embodiments and advantages related to the first aspect of the invention apply mutatis mutandis to this aspect of the invention.

[0067] In another related aspect, the invention provides a metal organic framework (MOF) comprising i. a plurality of metal ions, the plurality of metal ions consisting of ions of a metal selected from the group consisting of: zinc, zirconium, iron and aluminium; and ii. a plurality of organic ligands, the plurality of organic ligands comprising a) an organic ligand derived from a compound of Formula I;b) one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III, preferably the or each further organic ligand is derived from a compound of Formula II; andc) optionally, an organic ligand derived from the group consisting of 1H- 1,2,4-triazole, 2H-l,2,3-trizaole, lH-l,2,3-triazole, and combinations thereof; wherein each R1is independently selected from the group consisting of -CF3, CHF2, R4, NH2, substituted amino, Cl, Br, I, NO2, C(O)R4, OH, aryl, substituted aryl;wherein each R2and each R3is independently selected from the group consisting of Br, Cl, I, F, CF3, CHF2, NH2, substituted amino, NO2, R4, CO2R4, CO2H, CONH2, SH, and CN; wherein R4is Ci to C4 alkyl or substituted Ci to C4 alkyl; wherein m = 0, 1 or 2 wherein n = 1 or 2; and wherein p = 1 or 2.

[0068] In a second aspect, the invention provides a metal organic framework (MOF) body or bodies comprising metal organic framework as defined in the first or related aspects, and binder. The MOF body(ies) may be prepared by any method known to the skilled person, including the method described herein.

[0069] The or each MOF body may comprise binder. Herein, binder may refer to one binder or one or more binders. The or each MOF body may comprise a single species of binder. The MOF or each MOF body may comprise one or more species of binder. The or each MOF body may comprise a combination of binders. The or each MOF body may comprise less than about 45% total binder, preferably less than about 40% total binder, preferably less than about 35% total binder, preferably less than about 30% total binder, preferably less than about 25% total binder, preferably less that about 20% total binder, preferably less than about 15% total binder, preferably less than about 10% total binder, preferably less than about 5% total binder by weight of the or each MOF body. The or each MOF body may comprise greater than about 1% total binder, preferably greater than about 3% total binder, preferably greater than about 5% total binder or preferably greater than about 10% total binder by weight of the or each MOF body. The or each MOF body may comprise from about 1% to about 45%, preferably from about 3% to about 40%, preferably from about 5% to about 35%, preferably from about 10% to about 35%, preferably from about 10% to about 30%, preferably from about 15% to about 25%, preferably from about 20% to about 25%, total binder by weight of the or each MOF body.

[0070] The or each binder may be any material that is used to hold MOF crystallites together to form the MOF body. The or each binder may also act to adhere MOF crystallites to othermaterials, such as those being used as substrates. The MOF crystallites may be adhered to each other with the binder(s). The binder(s) may be water soluble or water insoluble.

[0071] Preferably, the or each binder may be an inorganic binder, an organic binder or a combination thereof. The inorganic binder(s) may be alumina (aluminium oxide), such as hydrated alumina, Bentonite and other clays, Lime (Calcium Oxide), Silica (Silicon Dioxide), Portland Cement, Gypsum (Calcium Sulfate), Sodium Silicate, Magnesium Oxide, Iron Oxide, Zinc Oxide, and combinations thereof.

[0072] The organic binder(s) may be a polymeric organic binder(s). Preferably, the binder(s) is polymeric organic binder(s). The polymeric organic binder may be selected from the group consisting of: polyvinyl alcohol, polyvinyl acetate, polyvinyl butyrate, polyethyleneimine, polyvinyl pyrrolidone, polyimide (PI), polyvinyl formal, polyurethane, epoxide, polycarboxylate, polyacrylic acid and salts thereof, such as polyacrylate, polylactic acid and derivatives thereof, graphene, graphene oxide, polypropylene glycol, poly(l,4-phenylene- ether-ether-sulfone) (PFEES), poly(tetrahydrofuran) (PTHF), polysulfone, poly-ethylene oxide polymers including block co-polymers such as PEO-PPO block co-polymers, polyolefin, polyamide, polysaccharides such as chitosan and celluloses including cellulose acetate, cellulose acetate esters such as cellulose acetate propionate and cellulose acetate butyrate, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP), polymers containing silane moieties, cross-linking agent such as hypophosphite, and any combination thereof. For the avoidance of doubt, the polymeric organic binder species, such as polyacrylic / polyacrylate, polyurethane and epoxide, may comprise moieties with cross-linking functionality and be capable of acting as cross-linking binders. References to polymeric organic binder includes references to that polymeric organic binder having cross-linking functionality. Preferably, the polymeric organic binder is selected from the group consisting of polyvinyl alcohol (PVA), polyimide, polyamide, polyvinyl pyrrolidone, epoxide, polycarboxylate and polyacrylic / polyacrylate, polyurethane, polylactic acid and derivatives thereof, polysaccharides including cellulose-based polymers such as cellulose acetate, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose phthalate, and combinations thereof.

[0073] Particularly preferred binders may be selected from the group consisting of cellulose- based polymers including methyl cellulose, polyacrylate, epoxide, polyurethane, PVA and combinations thereof. The organic polymeric binder(s) may include moieties capable of crosslinking reactions as well as cross-linking aids. Optionally, the binder may comprise methylcellulose in combination with a polyurethane and / or PVA. Optionally, the binder may be PVA and / or methyl cellulose in combination with epoxide and / or polyacrylate.

[0074] Preferably, the binder comprises at least one cellulose-based polymer and / or PVA and at least one organic polymer selected from the group consisting of epoxide, polyacrylate and polyurethane.

[0075] Typically, the or each MOF body comprises greater than about 55% MOF, or greater than about 60% MOF, or greater than about 70% MOF, or greater than about 75% MOF, or greater than about 80% MOF, or greater than about 85% MOF, or greater than about 90% MOF, or greater than about 95% MOF, by weight of the or each MOF body. Typically, the or each MOF body comprises less than about 99% MOF, or less than about 97% MOF, or less than about 95% MOF, or less than about 90% MOF, by weight of the or each MOF body. The or each MOF body may comprise from about 55% to about 99%, preferably from about 60% to about 97%, preferably from about 70% to about 95%, preferably from about 75% to about 90%, preferably from about 80% to about 85%, MOF by weight of the or each MOF body.

[0076] Preferably, the MOF crystallites are adhered to each other with binder.

[0077] The or each MOF body may be an extrudate, a milled granule, a tablet, an agglomerate, a coated substrate or a coating. The use of the MOF is not limited by the nature of the body and in some applications the MOF body comprises a non-MOF substrate to which a coating of the MOF of the first or related aspects of the invention, and optionally binder has been applied. Optionally, the or each MOF body is an extrudate having an aspect ratio of from about 1 to about 7. Preferably, the aspect ratio is from about 2 to about 6 or from about 3 to about 5. The aspect ratio is the ratio of the length of a particle (e.g. extrudate) to the width of the particle (e.g. extrudate). Alternatively, or additionally, the, or each, MOF body may be anextrudate having a cross-sectional diameter of from about 1 mm to about 5 mm, or from about 2 mm to about 4 mm. The aspect ratio and cross-sectional diameter are measured according to the method described herein.

[0078] Optional ly, the, or each, MOF body is a milled body having a mean body size of greater than about 0.25 mm, preferably greater than about 0.4 mm. Optionally, the, or each, MOF body is a milled body having a mean body size of less than about 1 mm, or less than about 0.8 mm. Optionally, the or each MOF body is a milled body having a mean body size of from about 0.25 mm to about 1 mm, preferably from about 0.4 mm to about 0.8 mm. The mean body size is measured according to the method described herein.

[0079] The, or each, MOF body may have a relative density of greater than about 0.4, or greaterthan about 0.5, orgreaterthan about 0.6, orgreaterthan about 0.7, of the theoretical, single-crystal density. The relative density of a MOF body is the envelope density of the body divided by the single-crystal density of the MOF.

[0080] Preferably, the, or each, MOF body has a relative density of from about 0.4 to about 1.2, or from about 0.7 to about 1.1, or from about 0.8 to about 1.0. If the envelope density of an adsorbent body is greaterthan the crystal density (i.e., the relative density is > 1), then this is likely due to the collapse of internal pores or non-porous defects or impurities. The greater the relative density is above 1, the more the internal pores will have been collapsed and the lower the sorption capacity. Limiting high relative density is necessary to avoid inefficient internal pore collapse. However, the relative density of an adsorbent body should typically not be very low as this typically indicates excessive levels of undesirable larger macropores.

[0081] Typically, the, or each, MOF body has an envelope density of greater than about 0.3 g / cm3, orgreaterthan about 0.4 g / cm3, orgreaterthan about 0.6g / cm3, orgreater than about 0.8 g / cm3, or greater than about 1.0 g / cm3. The or each MOF body may have an envelope density of less than about 2.0 g / cm3, or less than about 1.4 g / cm3, or less than about 1.2 g / cm3. Preferably, the or each MOF body has an envelope density of from about 0.3 g / cm3to about 2.0 g / cm3, preferably from about 0.4 g / cm3to about 1.4 g / cm3, preferably from about0.6 g / cm3to about 1.2 g / cm3, preferably from about 0.8 g / cm3to about 1.0 g / cm3. The envelope density is measured as described herein.

[0082] Preferably, the, or each, MOF body has a microporosity of greater than about 20%, or greater than about 30%, or greater than about 40%, of the total pore volume as measured by N2 adsorption at 77K. Preferably, the, or each, MOF body has a microporosity of less than about 75% of the total pore volume as measured by N2 adsorption at 77K. Preferably, the of each MOF body has a microporosity of from about 20% to about 75%, preferably from about 30% to about 70%, preferably from about 40% to about 60%, of the total pore volume as measured by N2 adsorption at 77K.

[0083] The, or each, MOF body may comprise a material selected from the group consisting of: nanoparticles of metal(s) and metal salt(s), enzyme(s), magnetic material(s), dye(s) and pigment(s), graphene, and any combination thereof.

[0084] Suitable nanoparticles include metal and metal oxide nanoparticles selected from Pd, Au, Ru, Rh, Pt, Fe, Sn, Zn, Ti, Pd and any combination thereof. The nanoparticles can be photoactive, such as being photo-catalytically active. Photoactive nanoparticles can include perovskite(s), especially halogen perovskite(s). Nanoparticles can be embedded in the MOF body where they can help bind MOF crystallites together or can be encapsulated within the MOF crystallites. If any nanoparticles are present, then their total level in the MOF body is usually less than about 0.15% volume of the MOF body.

[0085] In a third aspect, the invention provides a MOF-coated non-MOF substrate or substrate body or bodies. The or each MOF-coated non-MOF substrate body comprises a non-MOF substrate body(ies) and MOF composition. The MOF composition comprises metal organic framework as defined in the first or related aspects of the invention, optionally in the form of crystallites. Optionally, the MOF composition may comprise binder(s) (one or more binder species) as defined herein, for example less than about 45% total binder, preferably less than about 40% total binder, preferably less than about 30% total binder, preferably less than about 20% total binder, preferably less than about 10% total binder, by weight of the MOF composition. The MOF composition may comprise greater than about 1% total binder,preferably greater than about 3% total binder, preferably greater than about 5% total binder or preferably greater than about 10% total binder by weight of the MOF composition. The MOF composition may comprise from about 1% to about 45%, preferably from about 3% to about 40%, preferably from about 5% to about 35%, preferably from about 10% to about 35%, preferably from about 10% to about 20%, total binder by weight of the MOF composition.

[0086] Typically, the MOF composition comprises greater than about 55% MOF, or greater than about 60% MOF, or greater than about 70% MOF, or greater than about 75% MOF, or greater than about 80% MOF, or greater than about 85% MOF, or greater than about 90% MOF, or greater than about 95% MOF, by weight of the MOF composition. Typically, the MOF composition comprises less than about 99% MOF, or less than about 97% MOF, or less than about 95% MOF, or less than about 90% MOF, by weight of the MOF composition. The MOF composition may comprise from about 55% to about 99%, preferably from about 60% to about 97%, preferably from about 70% to about 95%, preferably from about 75% to about 90%, preferably from about 80% to about 85%, MOF by weight of the MOF composition.

[0087] Optionally, the MOF composition may comprise MOF in addition to MOF as defined in the first or related aspects of the invention. For example, the MOF composition may additionally comprise MOF such as MOF having terephthalic acid-based ligand.

[0088] The external surface of the or each substrate body is at least partially coated with MOF composition. Preferably, the external surface of the or each substrate body is substantially entirely (or entirely) coated with MOF composition.

[0089] The MOF composition coating around the or each substrate body may be present at a depth of from about 10 microns (pm) to about 400 microns orfrom about 50 microns to about 400 microns or from about 75 microns to about 300 microns or from about 100 microns to about 200 microns or from about 10 microns (pm) to about 100 microns (pm). The depth of the MOF composition coating around the or each substrate body is measured by scanning electron microscopy (SEM) as described herein.

[0090] The depth of the MOF composition coating around the or each substrate body may be uniform or irregular. Preferably, the depth of the MOF composition coating around the oreach substrate body is uniform.

[0091] Partially coating or substantially entirely (or entirely) coating of the or each substrate body with MOF composition may be advantageous in separation processes because the thin coating layers can be used to achieve improved mass transfer kinetics and lower pressure drops across a structured adsorbent bed. This represents a significant cost and energy saving.

[0092] A single MOF-coated non-MOF substrate body may comprise one or more non-MOF substrate bodies which are coated with the MOF composition. That is, more than one non- MOF substrate bodies may be together coated with MOF composition to form one MOF coated body. Alternatively, a single non-MOF substrate body may be coated with MOF composition to form one MOF coated body.

[0093] The non-MOF substrate is not metal organic framework (MOF). The substrate may be an inert material and / or a material having chemical activity. Preferably the substrate is thermally conductive. Preferably the substrate is electrically conductive. For example, the substrate may be selected from the group consisting of: alumina, cordierite, stainless steel, aluminium, carbon, conductive ceramics (such as indium tin oxide), Yttria-stabilized zirconia (YSZ), carbon fibre, organic polymers such as polyethylene, polypropylene and combinations thereof. The substrate may be porous or non-porous. The substrate may be a parallel channel contactor.

[0094] The substrate may be flexible or the substrate may be rigid. The substrate may be planar, such as a planar sheet. Thus, the MOF composition may be coated onto one or both of the two planar surfaces of the planar sheet. The planar substrate may comprise apertures. The planar substrate may comprise a mesh. The planar substrates may be stacked together to form larger adsorbent substrate assemblies, in this embodiment the term substrate includes substrate assembly.

[0095] The substrate may comprise a series of substantially parallel or parallel channels. The substantially parallel or parallel channels may have a cross-sectional channel diameter of from about 0.1 mm to about 5 mm, preferably from about 0.5 mm to about 4 mm, preferably from about 1 mm to about 3 mm. The shape of the substantially parallel or parallel channels may be square, hexagonal or circular. The substantially parallel or parallel channels may be formed from corrugation of the substrate, for example, corrugation of planar sheets of the substrate to provide e.g. sinusoidal channels. Alternatively they may be formed by extrusion of substrate material(s) through suitable die-plates followed by cutting and drying to form monoliths comprising the substantially parallel or parallel channels. It is well within the remit of the skilled person to identify an appropriate method of preparing substrates having substantially parallel or parallel channels. The substrate body(ies) or monolith(s) comprising the substantially parallel or parallel channels may have a cross-sectional diameter of from about 1 cm to about 3 cm. The substantially parallel or parallel channels may have a consistent cross- sectional shape. 'Parallel channel' used herein means channels which are side by side, having the same distance continuously between them. By "substantially parallel channel" is meant that the channel deviates from 'true' parallel by less than about 1°, preferably less than about 0.5°, preferably less than about 0.1°.

[0096] The MOF composition may be coated onto the substrate body, including on the surface of the substrate body in the parallel channels.

[0097] Additionally, or alternatively, the or each substrate body may be a solid extrudate without any internal substantially parallel or parallel channels. The or each substrate body may then be coated with MOF composition. Such MOF-coated non-MOF body(ies) may have an aspect ratio of from about 1 to about 7. Preferably, the aspect ratio is from about 2 to about 6 or from about 4 to about 5. The aspect ratio is the ratio of the length of a body (e.g. substrate body) to the width of the body (e.g. substrate body). Alternatively, or additionally, the or each MOF-coated substrate body may be an have a cross-sectional diameter of from about 1 mm to about 5 mm, or from about 2 mm to about 4 mm. The aspect ratio and cross-sectional diameter are measured according to the method described herein.

[0098] Optional ly, the or each MOF-coated body may be approximately spherical or spherical and have a mean body size of greater than about 0.25 mm, preferably greater than about 0.4 mm, preferably greater than about 1.0 mm. Optionally, the or each MOF-coated substrate body is a body having a mean body size of less than about 2 mm, or less than about 1.5 mm. The mean body size is measured according to the method described herein.

[0099] For the avoidance of doubt, embodiments related to the first (and related) and second aspects of the invention apply mutatis mutandis to the third aspect of the invention.

[0100] In a fourth aspect, the invention provides a composition comprising metal organic framework as defined in the first or related aspects, MOF body(ies) as defined in the second aspect, MOF-coated non-MOF substrate body or bodies according to the third aspect, or combinations thereof.

[0101] The composition may comprise at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90% of metal organic framework by weight of the composition.

[0102] The composition may comprise less than about 97%, or less than about 95%, or less than about 90%, or less than about 80%, of metal organic framework by weight of the composition.

[0103] The composition may comprise from about 50% to about 99%, or from about 60% to about 97%, or from about 70% to about 95%, or from about 80% to about 90%, of metal organic framework by weight of the composition.

[0104] The composition may comprise at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90%, or at least about 95%, or at least about 97%, or at least about 99%, of the or each MOF body by weight of the composition.

[0105] The composition may comprise less than about 99%, or less than about 97%, or less than about 95%, or less than about 90%, or less than about 80%, of the or each MOF body by weight of the composition.

[0106] The composition may comprise from about 50% to about 99%, or from about 60% to about 97%, or from about 70% to about 95%, or from about 80% to about 90%, of the or each MOF body by weight of the composition.

[0107] The composition may comprise at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90%, or at least about 95%, or at least about 97%, or at least about 99%, of the or each MOF-coated non-MOF substrate body by weight of the composition.

[0108] The composition may comprise less than about 99%, or less than about 97%, or less than about 95%, or less than about 90%, or less than about 80%, of the or each MOF-coated non-MOF substrate body by weight of the composition.

[0109] The composition may comprise from about 50% to about 99%, or from about 60% to about 97%, or from about 70% to about 95%, or from about 80% to about 90%, of the or each MOF-coated non-MOF substrate body by weight of the composition.

[0110] The composition may have a bulk density of about 0.3 g / cm3or greater, for example about 0.5 g / cm3or greater, such as about 0.6 g / cm3or greater, for example about 0.7 g / cm3or greater, such as about 0.8 g / cm3or greater, for example about 0.9 g / cm3or greater. The composition may have a bulk density of from about 0.3 g / cm3to about 1.4 g / cm3, preferably from about 0.5 g / cm3to about 1.2 g / cm3, preferably from about 0.6 g / cm3to about 1.0 g / cm3, preferably from about 0.7 g / cm3to about 0.9 g / cm3. The bulk density may be defined as the mass of the MOF bodies or MOF-coated non-MOF substrate bodies divided by the total volume occupied by those MOF bodies or MOF-coated non-MOF substrate bodies, or in other words the mass of the composition divided by the total volume occupied by the composition.

[0111] For the avoidance of doubt, the 'bulk density' may refer to the 'untapped density' (i.e. the density of the material or powder as freely settled) or the 'tapped density' (i.e. the maximum density achieved when the material is tapped under specific conditions). Preferably, the bulk density is the tapped density.

[0112] The untapped density and the tapped density may be similar. For example, extrudates typically have high aspect ratios and poor packing, and therefore tapping may have little effect on the bulk density.

[0113] The composition may consist essentially of MOF of the first or related aspects, MOF body(ies) of the second aspect, MOF-coated non-MOF substrate body(ies) of the third aspect or combinations thereof; that is further components may be present in the composition, but only those not materially affecting the essential characteristics of the composition. Alternatively, the composition may consist of MOF of the first or related aspects, MOF body(ies) of the second aspect, MOF-coated non-MOF substrate body(ies) of the third aspect, or combinations thereof. Preferably, the composition may comprise an additive.

[0114] The composition may be provided as a solid or an aqueous suspension.

[0115] For the avoidance of doubt, embodiments related to the first (and related) to third aspects of the invention apply mutatis mutandis to the fourth aspect of the invention.

[0116] In a fifth aspect, the invention provides a structured adsorbent bed comprising metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or combinations thereof.

[0117] The structured absorbent bed may comprise a frame made from alumina, ceramic materials, or metal (such as stainless steel). Alternatively, the structured adsorbent bed may not comprise a frame and may instead be formed from MOF as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect,or combinations thereof. For example, the shape and / or structure of the structured adsorbent bed may be defined by MOF as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or combinations thereof. The structured adsorbent bed or the frame of the structured adsorbent bed may be porous to CO2.

[0118] The structured adsorbent bed may comprise a support which may be a three- dimensional material, which acts as a support in the structured adsorbent bed for metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or combinations thereof. The support may be a solid material, which may comprise apertures, or may be a honeycomb structure. The support may comprise alumina, metal (such as stainless steel) or ceramic materials.

[0119] The support may comprise a series of substantially parallel or parallel channels. The parallel or substantially parallel channels may have a channel diameter of from about 0.1 mm to about 5 mm, preferably from about 0.5 mm to about 4 mm, preferably from about 1 mm to about 2 mm. The shape of the or each substantially parallel or parallel channels may be square, hexagonal or circular. The parallel or substantially parallel channels may be formed from corrugation of the support, for example, corrugation of sheets of the support to provide e.g. sinusoidal channels. The parallel or substantially parallel channels may have a consistent cross-sectional shape.

[0120] Alternatively or additionally, the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or combinations thereof may be included in the structured adsorbent bed without a support. For example, the MOF-coated non-MOF substrate body or bodies may be formed having dimensions appropriate to fit in or form the structured adsorbent bed.

[0121] In the structured adsorbent bed, the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or combinations thereof may have a bulk density of about 0.3 g / cm3or greater, for example about 0.5 g / cm3or greater, such as about 0.6 g / cm3or greater, for example about 0.7 g / cm3or greater, such as about 0.8 g / cm3or greater, for example about 0.9 g / cm3or greater. The metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or combinations thereof may have a bulk density of from about 0.3 g / cm3to about 1.4 g / cm3, preferably from about 0.5 g / cm3to about 1.2 g / cm3, preferably from about 0.6 g / cm3to about 1.0 g / cm3, preferably from about 0.7 g / cm3to about 0.9 g / cm3.

[0122] The structured adsorbent bed may be a size suitable for the application, it is well within the remit of the skilled person to select an appropriate size forthe structured adsorbent bed and / or the substrate.

[0123] For the avoidance of doubt, embodiments related to the first (and related) to fourth aspect of the invention apply mutatis mutandis to the fifth aspect of the invention.

[0124] In a sixth aspect, the invention provides a method of producing metal organic framework as defined in the first or related aspects, the method comprising the steps of: (a) providing a first solution comprising metal ion precursor; (b) providing a second solution comprising one or more organic ligand precursors derived from compound of Formula I, one or more further organic ligand precursors derived from compound selected from the group consisting of Formula II, Formula III, and combinations thereof, and optionally organic ligand precursor derived from the group consisting of lH-l,2,4-triazole, 2H-l,2,3-trizaole, 1H-1,2,3- triazole, or combinations thereof; and (c) mixing the first solution and second solution to form metal organic framework.

[0125] The metal ion precursor may be a metal salt. For example, when the metal ion is zinc ion then the metal ion precursor may be zinc carbonate basic or zinc acetate dihydrate. The skilled person is well aware of appropriate metal ion precursors to provide the required metal ion in the MOF of the present invention.

[0126] The first solution may comprise a solvent selected from the group consisting of water, methanol, dimethylsulfoxide (DMSO), dimethylformamide (DMF), diethylformamide (DEF), tetra hydrofuran (THF), dimethylacetamide (DMA), acetonitrile, dilute nitric acid, and combinations thereof. The second solution may comprise a solvent selected from the group consisting of water, ethanol, methanol, DMSO, DMF, DEF, THF, DMA, acetonitrile, dilute nitric acid, and combinations thereof.

[0127] Step (c) may be carried out at from about 20 °C to about 120 °C, preferably from about 25 °C to about 110 °C, preferably from about 30 °C to about 100 °C, preferably from about 40 °C to about 90 °C, preferably from about 50 °C to about 80 °C, preferably from about 60 °C to about 70 °C. Step (c) may be carried out at room temperature.

[0128] Alternatively or additionally, in step (c), the first solution and second solution may be mixed to form a reaction mixture, wherein the reaction mixture may be heated to a temperature of about 70 °C to about 120 °C, preferably about 80 °C to about 110 °C, preferably about 90°C to about 100 °C.

[0129] Step (c) may carried out for from about 5 hours to about 24 hours, preferably from about 7 hours to about 20 hours, preferably from about 10 hours to about 16 hours, preferably from about 12 hours to about 14 hours. For example, the reaction mixture may be heated for from about 5 hours to about 24 hours, preferably from about 7 hours to about 20 hours, preferably from about 10 hours to about 16 hours, preferably from about 12 hours to about 14 hours.

[0130] Step (c) may be carried out in high boiling point solvents such as dimethylformamide, diethylformamide, dimethylacetamide, or combinations thereof. Using such solvents, step (c) may be carried out in an autoclave or screw-capped vials at elevated temperatures, for example from about 100 °C to about 250 °C, preferably from about 150 °C to about 200 °C.

[0131] Once formed, the metal organic framework may be separated from the reaction mixture by filtration or centrifugation, preferably centrifugation. Once solid MOF is isolated, it may be washed with a solvent for example, methanol or ethanol, and dried in air at fromabout 15 °C to about 30 °C, preferably from about 20 °C to about 25 °C for about 1 hour to about 24 hours, preferably from about 2 hours to about 20 hours, preferably from about 4 hours to about 15 hours, preferably from about 6 hours to about 10 hours.

[0132] Once formed, the MOF may be post-synthetically functionalised at e.g. an amino group to introduce a substituted amino group as described herein. The appropriate reaction conditions to post-synthetically functionalise the MOF are well within the common general knowledge of the skilled person.

[0133] The MOF may be activated under N2 flow or vacuum, preferably N2 flow. The MOF may be activated at from about 100 °C to about 200 °C, preferably from about 120 °C to about 180 °C, preferably from about 140 °C to about 160 °C, preferably about 150 °C for about 6 hours to about 15 hours, preferably from about 8 hours to about 12 hours.

[0134] The MOF may be isolated by centrifugation or filtration, preferably centrifugation. The isolated MOF may be dried in air or under vacuum, preferably at room temperature.

[0135] The metal ion precursor may be provided in the first solution at a concentration of from about 0.07 M to about 0.25 M, preferably from about 0.1 M to about 0.2 M, preferably from about 0.12 M to about 0.15 M. The organic ligand compounds may be provided in the first solution at a concentration of from about 0.6 M to about 2 M, preferably from about 0.8 M to about 1.8 M, preferably from about 1 M to about 1.5 M. The Inventors have found that this preparation of the MOF can be carried out at varying concentrations, including at high and low concentration. The skilled person is well able to identify appropriate reaction conditions for the preparation of certain MOFs.

[0136] For the avoidance of doubt, embodiments related to the first (and related) to fifth aspect of the invention apply mutatis mutandis to the sixth aspect of the invention.

[0137] In a seventh aspect, the invention provides a method of producing metal organic framework as defined in the first or related aspects, the method comprising the steps of: (a) providing a first solution comprising one or more organic ligand precursors derived from compound of Formula I and one or more further organic ligand precursor derived fromcompound selected from the group consisting of Formula II, Formula III, and combinations thereof; (b) providing a metal ion precursor, optionally in solid form; and (c) contacting the metal ion precursor with the first solution form metal organic framework.

[0138] The metal ion precursor is as defined in relation to the sixth aspect.

[0139] The first solution may comprise a solvent selected from the group consisting of water, methanol, dimethylsulfoxide (DMSO), dimethylformamide (DMF), diethylformamide (DEF), tetra hydrofuran (THF), dimethylacetamide (DMA), acetonitrile, dilute nitric acid, and combinations thereof.

[0140] Step (c) may be carried out at from about 20 °C to about 120 °C, preferably from about 25 °C to about 110 °C, preferably from about 30 °C to about 100 °C, preferably from about 40 °C to about 90 °C, preferably from about 50 °C to about 80 °C, preferably from about 60 °C to about 70 °C. Step (c) may be carried out at room temperature.

[0141] Alternatively or additionally, in step (c), the contacting may form a reaction mixture, wherein the reaction mixture may be heated to a temperature of about 70 °C to about 120 °C, preferably about 80 °C to about 110 °C, preferably about 90°C to about 100 °C.

[0142] Step (c) may carried out for from about 5 hours to about 24 hours, preferably from about 7 hours to about 20 hours, preferably from about 10 hours to about 16 hours, preferably from about 12 hours to about 14 hours. For example, the reaction mixture may be heated for from about 5 hours to about 24 hours, preferably from about 7 hours to about 20 hours, preferably from about 10 hours to about 16 hours, preferably from about 12 hours to about 14 hours.

[0143] Step (c) may be carried out in high boiling point solvents such as dimethylformamide, diethylformamide, dimethylacetamide, or combinations thereof. Using such solvents, step (c) may be carried out in an autoclave or screw-capped vials at elevated temperatures, for example from about 100 °C to about 250 °C, preferably from about 150 °C to about 200 °C.

[0144] Once formed, the metal organic framework may be separated from the reaction mixture by filtration or centrifugation, preferably centrifugation. Once solid MOF is isolated, it may be washed with a solvent for example, methanol or ethanol, and dried in air at from about 15 °C to about 30 °C, preferably from about 20 °C to about 25 °C for about 1 hour to about 24 hours, preferably from about 2 hours to about 20 hours, preferably from about 4 hours to about 15 hours, preferably from about 6 hours to about 10 hours.

[0145] Once formed, the MOF may be post-synthetically functionalised at e.g. an amino group to introduce a substituted amino group as described herein. The appropriate reaction conditions to post-synthetically functionalise the MOF are well within the common general knowledge of the skilled person.

[0146] The MOF may be activated under N2 flow or vacuum, preferably N2 flow. The MOF may be activated at from about 100 °C to about 200 °C, preferably from about 120 °C to about 180 °C, preferably from about 140 °C to about 160 °C, preferably about 150 °C for about 6 hours to about 15 hours, preferably from about 8 hours to about 12 hours.

[0147] The MOF may be isolated by centrifugation or filtration, preferably centrifugation. The isolated MOF may be dried in air or under vacuum, preferably at room temperature.

[0148] The Inventors have found that this preparation of the MOF can be carried out at varying concentrations, including at high and low concentration. The skilled person is well able to identify appropriate reaction conditions for the preparation of certain MOFs.

[0149] For the avoidance of doubt, embodiments related to the first (and related) to sixth aspect of the invention apply mutatis mutandis to the seventh aspect of the invention.

[0150] Advantageously, the method of the sixth aspect allows the use of low cost, readily available raw materials to produce MOFs suitable for gas, e.g. CO2, capture applications.

[0151] In a further aspect, the invention also provides metal organic framework produced by the method of the sixth or seventh aspect.

[0152] For the avoidance of doubt, embodiments related to the first aspect of the invention apply mutatis mutandis to the sixth or seventh aspect of the invention.

[0153] In an eighth aspect, the invention provides the use of the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or a structured adsorbent bed as defined in the fifth aspect in carbon dioxide adsorption. Preferably, the use of the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or a structured adsorbent bed as defined in the fifth aspect in high concentration carbon dioxide adsorption. The invention also provides the use of the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or a structured adsorbent bed as defined in the fifth aspect in removing CO2 directly from the flue gas of an industrial process, such as the flue gas of a thermal power plant or cement works.

[0154] In an ninth aspect, the invention provides the use of the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or a structured adsorbent bed as defined in the fifth aspect in gas separation. The gas separation may be separation of Kr from a mixture of Kr / CF Nz, to obtain pure Kr from a mixture of Kr, CF4 and N2.

[0155] In a tenth aspect, the invention provides the use of the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or a structured adsorbent bed as defined in the fifth aspect in water adsorption. The water adsorption may be water harvesting or heating, ventilation, and air conditioning (HVAC).

[0156] In an eleventh aspect, the invention provides the use of the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or a structured adsorbent bed as defined in the fifth aspect in catalysis.

[0157] In a twelfth aspect, the invention provides the use of the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or a structured adsorbent bed as defined in the fifth aspect in a gas separation process. Preferably, the gas separation process may be selected from the group consisting of carbon dioxide capture, krypton recovery, krypton purification, and combinations thereof.

[0158] In a thirteenth aspect, the invention provides the use of the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or a structured adsorbent bed as defined in the fifth aspect in hydrogen storage.

[0159] In a fourteenth aspect, the invention provides the use of the metal organic framework as defined in the first or related aspects, MOF body or bodies as defined in the second aspect, MOF-coated non-MOF substrate body or bodies as defined in the third aspect, a composition as defined in the fourth aspect, or a structured adsorbent bed as defined in the fifth aspect in hydrocarbon purification.

[0160] For the avoidance of doubt, embodiments related to the first (and related) to fifth aspects of the invention apply mutatis mutandis to the eighth to fourteenth aspect of the invention.

[0161] For the avoidance of doubt, embodiments related to each aspect of the invention apply mutatis mutandis to the other aspects of the invention. Further aspects and embodiments of the present invention will be evident from the discussion herein.Brief Description of the DrawingsFigure 1 (a) 21 °C CO2 adsorption isotherm for IMM-33, IMM-34 and IMM-35 and (b) log plot of 21 °C CO2 adsorption isotherm for IMM-33, IMM-34 and IMM-35.Figure 2 (a) 77K N2 adsorption isotherm analysis for IMM-33 (circles), IMM-34 (triangles) and IMM-35 (diamonds) and (b) 21 °C N2 adsorption isotherm analysis for IMM-34.Figure 3 Powder X-ray diffraction (PXRD) analysis of IMM-33, IMM-34 and IMM-35.Figure 4 Thermogravimetric analysis (TGA) of IMM-33, IMM-34 and IMM-35.Figure 5 Water sorption of IMM-33 (circles), IMM-34 (triangles) and IMM-35 (diamonds) at 25 °CFigure 6 Water adsorption isotherms at 25 °C and 70 °C for (a) IMM-33, (b) IMM-34 and (c) IMM-35.Figure 7 21 °C CO2 adsorption analysis for (a) IMM-33, (b) IMM-34 and (c) IMM-35 before and after exposure to 99% relative humidity for one week at room temperature.Figure 8 (a) Room temperature CO2 adsorption isotherm for IMM-33, IMM-34 and IMM-35 powder samples at 15% CO2 concentration and (b) log plot of room temperature CO2 adsorption isotherm for IMM-33, IMM-34 and IMM-35 powder samples at 15% CO2 concentration.Figure 9 Water sorption of IMM-33, IMM-34 and IMM-35 powder at (a) 25 °C and (b) 70 °C.Figure 10 (a) Room temperature CO2 adsorption isotherm for IMM-33, IMM-34 and IMM-35 body samples at 15% CO2 concentration and (b) log plot of room temperature CO2 adsorption isotherm for MOF-31 and MOF-32 body samples at 15% CO2 concentration.Figure 11 (a) Steam stability of IMM-34 body at 140 °C over 4 weeks and (b) log plot of steam stability of IMM-34 body at 140 °C over 4 weeks.Figure 12 (a) Room temperature CO2 adsorption analysis for IMM-34 body before and after exposure to 70% relative humidity for 4 weeks at room temperature (15% CO2 / 85% N2) and (b) log plot of room temperature CO2 adsorption analysis for IMM-34 body before and after exposure to 70% relative humidity for 4 weeks at room temperature (15% CO2 / 85% N2).Figure 13 Room temperature CO2 adsorption isotherm for IMM-34 body before and after exposure to a pH 5 H2SO4 solution for 24 hours.Detailed Description of the Invention

[0162] References herein to a singular of a noun encompass the plural of the noun, and vice- versa, unless the context implies otherwise.

[0163] Throughout this specification the word 'comprise', or variations such as 'comprises' or 'comprising', will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps. The term 'comprising' includes within its ambit the term 'consisting' or 'consisting essentially of'.

[0164] The term 'consisting' or variants thereof is to be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, and the exclusion of any other element, integer or step or group of elements, integers or steps.

[0165] The term 'consisting essentially of' or variants thereof is to be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, and that further components may be present, but only those not materially affecting the essential characteristics of the embodiment of the invention.

[0166] The term 'about' herein, when qualifying a number or value, is used to refer to values that lie within ± 5% of the value specified. For the avoidance of doubt, where a number or value is specified herein in the absence of the term 'about', the number or value should be understood according to standard numeric rounding conventions according to the number of decimal places. For example, a whole number, such as 6, is understood to encompass values > 5.5 and < 6.5. Likewise, a number specified to one decimal place, such as 5.3, is understood to encompass values > 5.25 and < 5.35.

[0167] Where a range of values is provided, the range includes the end point values. For example, the range 20 to 28, or from 20 to 28, would include the values 20, 21, 22, 23, 24, 25, 26, 27 and 28; the range 5 to 15, or from 5 to 15, would include the values 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15.

[0168] Throughout this application, the IUPAC definitions of micropores (diameter of < 2 nm), meso-pores (diameter of 2 nm - 50 nm) and macropores (diameter of > 50 nm) are used.

[0169] Metal-organic frameworks (MOFs) are materials consisting of coordination bonds between metal ions, e.g. metal cations, and multidentate organic ligands. The MOF structure is characterised by an open framework that may be porous. The metal cations and organic ligands are as described herein. MOFs are a class of porous polymers consisting of metal ions or clusters of metal ions coordinated to organic ligands to form one-, two- or three- dimensional structures.

[0170] "Organic ligand derived from a compound" means that the compound is deprotonated to enable coordination to the metal (e.g. zinc) ion. For example "organic ligand derived from 1,2,4-triazole" means 1,2,4-triazolate (Ligand 1) and "organic ligand derived from 3-methyl- lH-l,2,4-triazole" means 3-methyl-lH-l,2,4-triazolate (Ligand 2), and so on.« 2

[0171] The term "alkyl" is well known in the art and defines univalent groups derived from alkanes by removal of a hydrogen atom from any carbon atom, wherein the term "alkane" is intended to define acyclic branched or unbranched hydrocarbons having the general formula CnHjn+2, wherein n is an integer >1. The term "substituted alkyl" is well known in the art and refers to substitution of one or more hydrogen atoms of the alkyl moiety with a substituent or substituents, multiple degrees of substitution being allowed unless otherwise stated, provided that the substitution results in a stable or chemically feasible compound.

[0172] By "Ci to C4 alkyl" herein is meant any one alkyl group selected from the group consisting of methyl (Me, CH3), ethyl (Et, CH2CH3), n-propyl (n-Pr, CH2CH2CH3), iso-propyl (i-Pr,CH(CH3)2), n-butyl (n-Bu, CH2CH2CH2CH3), sec-butyl (s-Bu, CH(CH3)CH2CH3, R- or S-sec-butyl), iso-butyl (i-Bu, CH2CH(CH3)2) and tert-butyl (t-Bu, C(CH3)3).

[0173] As used herein, "substituted" refers to substitution of one or more hydrogen atoms of the designated moiety with the substituent or substituents, multiple degrees of substitution being allowed unless otherwise stated, provided that the substitution results in a stable or chemically feasible compound. A stable compound or chemically feasible compound is one in which the chemical structure is not substantially altered when kept at a temperature from about -80 °C to about +40 °C, in the absence of moisture or other chemically reactive conditions, for at least a week.

[0174] The substitution may be a heteroatom or a functional group comprising a heteroatom provided that valency is satisfied. The heteroatom(s) may be selected from the group consisting of nitrogen, sulfur and nitrogen. The heteroatom may replace -H or -CH2-. For example, one -H may be replaced by -SH, -SR4, -OH, -OR4, -NH2, -NHR4, or -N(R4)2. For example, two -H on the same carbon may be replaced by =S, =0, =NH or =NR4. For example, three -H on the same carbon may be replaced by N. For example, -CH2- may be replaced by -S-, -O-, - NH- or -NR4-. R4is as defined herein.

[0175] The term "aryl" is well known in the art and, as used herein, is intended to include C3- C12 aryl groups. The term "aryl" refers to both carbocyclic and heterocyclic aryl groups. The term "substituted aryl" refers to aryl groups wherein one or more of the hydrogen atoms of the aryl group are replaced by a substituent, such as Ci to C4 alkyl, substituted Ci to C4 alkyl, a heteroatom or a functional group containing a heteroatom.

[0176] When referring to MOF bodies, "body" / "bodies" may be used interchangeably with "monolith7"monoliths", and the like.

[0177] A method of preparing one or more MOF bodies as defined in the second aspect of the invention may comprise the steps of: (a) providing a first solution comprising metal ion precursor; (b) providing a second solution comprising one or more organic ligand precursors derived from compound of Formula I, one or more organic ligand precursors derived from compound selected from the group consisting of Formula II, Formula III, and combinationsthereof, and optionally organic ligand precursor derived from the group consisting of 1H-1,2,4- triazole, 2H-l,2,3-trizaole, lH-l,2,3-triazole, or combinations thereof; (c) mixing the first solution and second solution to form metal organic framework; (d) contacting the metal organic framework with binder(s) dissolved or dispersed in a solvent to provide one or more solvated MOF bodies; and (e) removing at least some of the solvent to form the one or more MOF bodies.

[0178] An alternative method of preparing one or more MOF bodies as defined in the second aspect of the invention may comprise the steps of: (a) providing a first solution comprising one or more organic ligand precursors derived from compound of Formula I, one or more further organic ligand precursors derived from compound selected from the group consisting of Formula II, Formula III, and combinations thereof, and optionally organic ligand precursor derived from the group consisting of lH-l,2,4-triazole, 2H-l,2,3-trizaole, lH-l,2,3-triazole, or combinations thereof; (b) providing a metal ion precursor, optionally in solid form; (c) contacting the metal ion precursor with the first solution to form metal organic framework; (d) contacting the metal organic framework with binder(s) dissolved or dispersed in a solvent to provide one or more solvated MOF bodies; and (e) removing at least some of the solvent to form the one or more MOF bodies.

[0179] Suitable conditions for steps (a) to (e), e.g. solvent, reaction temperature, reaction time, vary depending on the MOF materials, and such conditions will be within the ambit of the skilled person. Suitable conditions are described herein.

[0180] In step (e) the solvent may be partially or fully removed. The solvent may be removed from the solvated MOF bodies by any suitable means. For example, the solvent may be removed by freeze-drying, centrifugation, heating at high temperature (e.g. greater than about 100 °C), or a combination thereof.

[0181] The MOF bodies can be subjected to a size reduction step to reduce the size of the MOF bodies prior to use. Such a size reduction step, for example using a cutting mill, can produce smaller adsorbent bodies, such as bodies having a diameter of less than about 2 mm or even less than about 1 mm.

[0182] This method may be particularly advantageous as MOF bodies having optimal properties, such as improved stability and robustness, as well as a high density and high surface area, may be prepared even with low levels of binder.

[0183] A method of preparing one or more MOF-coated substrate bodies as defined in the third aspect of the invention may comprise the steps of: (a) forming MOF as defined in the first or related aspects of the invention, for example using the method of the sixth or seventh aspect of the invention; (b) dispersing the MOF in a solvent to provide a MOF suspension, optionally wherein binder(s) is dissolved or dispersed in the solvent; and (c) dip-coating one or more substrate bodies in the MOF suspension to form the one or more MOF-coated substrate bodies.

[0184] The solvent may be selected from the group consisting of: water, methanol, ethanol, dimethylformamide, dichloromethane, toluene, ethyl acetate, acetone, DMSO, and combinations thereof.

[0185] This method may be particularly advantageous as MOF-coated substrate bodies having optimal properties, such as improved stability and robustness, as well as a high density and high surface area, may be prepared even with no or low levels of binder.

[0186] Dip-coating step (c) may comprise the steps of immersion, start-up, deposition, drainage and evaporation. By immersion is meant the substrate body is immersed in the solution of the coating material (MOF) at a constant speed. By start-up is meant the substrate body has remained inside the solution for a period of time and is beginning to be pulled up and out of the solution. By deposition is meant the thin layer (coating) of MOF deposits on the substrate body while it is pulled up and out of the solution. The withdrawing (removal) from the solution is carried out at a constant speed to avoid any uneven distribution. The speed of withdrawal determines the thickness of the coating (faster withdrawal results in thicker coating material). By drainage is meant excess liquid will drain from the surface of the MOF-coated substrate body. By evaporation is meant the solvent evaporates from the liquid, forming the thin layer (coating) of MOF on the substrate body. For volatile solvents, such asalcohols, evaporation starts during the deposition and drainage steps. These steps may be repeated. Dip-coating may be a continuous process, i.e. the steps are carried out directly after each other.

[0187] The thickness of the coating can be controlled by a number of factors known to the skilled person. For example, the quality of the initial substrate surface, submersion time, withdrawal speed, number of dipping cycles, MOF solution composition, concentration and temperature, number of MOF solutions in each dipping sequence, and environment humidity. Advantageously, the dip coating technique can give uniform, high quality films even on bulky, complex shapes.

[0188] Every document cited herein, including any cross-referenced or related patent or application, is hereby incorporated by reference in its entirety unless expressly excluded or otherwise limited.

[0189] It will be appreciated that various modifications may be made to the embodiments shown without departing from the spirit and scope of the invention as defined by the accompanying claims.

[0190] The invention may be further understood with reference to the following non-limiting clauses and examples following thereafter:1. A metal organic framework (MOF) comprising a) a plurality of metal ions, each of the plurality of metal ions having a valency selected from the group consisting of +2 and +3; and b) a plurality of organic ligands, the plurality of organic ligands comprising i. organic ligand derived from a compound of Formula I;ii. one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III; andiii. optionally, organic ligand derived from the group consisting of 1H- 1,2,4-triazole, 2H-l,2,3-trizaole, lH-l,2,3-triazole, and combinations thereof; wherein each R1is independently selected from the group consisting of Cl, Br, I, F, CF3, CHF2, R4, NH2, substituted amino, Cl, Br, I, NO2, C(O)R4, OH, aryl, substituted aryl; wherein each R2and each R3is independently selected from the group consisting of Br, Cl, I, F, CF3, CHF2, NH2, substituted amino, NO2, R4, CO2R4, CO2H, CONH2, SH, and CN; wherein R4is Ci to C4 alkyl or substituted Ci to C4 alkyl; wherein m = 0, 1 or 2 wherein n = 1 or 2; and wherein p = 1 or 2. The metal organic framework according to clause 1 comprising organic ligand derived from a compound of Formula II. The metal organic framework according to clause 1 or clause 2 wherein n = 1 and R2is selected from the group consisting of 3-CI, 3-1, 3-NH2, 5-NH2, 3-Br, 5-Br, 3-CO2H, 3-CN, 3-C(O)NH2, 3-CO2CH3, 5-CO2CH2CH3, 3-CH3, 5-CH3, 3-CH2CH3, 5-CH2CH3, 3-CHF2, 3- CF3, 5-CF3, 3-SH, 3-NO2, and 5-NO2. The metal organic framework according to clause 1 or clause 2 wherein n = 2, and wherein (i) one R2is 3-NH2 and one R2is 5-NH2, (ii) one R2is 3-CI and one R2is 5-CI, (iii) one R2is 3-Br and one R2is 5-Br, (iv) one R2is 3-CH3 and one R2is 5-CH3, (v) one R2is 3-CN and one R2is 5-NH2, (vi) one R2is 3-C(O)OCH3 and one R2is 5-NH2, (vii) one R2is 3-SH and one R2is 5-CH3, (viii) one R2is 3-NH2 and one R2is 5-SH, (ix) one R2is 3- C(O)OCH3 and one R2is 5-Br, (x) one R2is 3-CO2H and one R2is 5-Br, (xi) one R2is 3- C(O)OCH2CH3 and one R2is 5-CI, (xii) one R2is 3-SH and one R2is 5-CF3, (xiii) one R2is 3-CO2H and one R2is 5-NH2, or (xiv) one R2is 3-NH2 and one R2is 5-CO2H.The metal organic framework according to clause 1 or clause 2, comprising one organic ligand derived from a compound of Formula II, wherein a) n = 1 and R2is 3-CHs; b) n = 1 and R2is 3-NH2; c) n = 1 and R2is 5-CH3; or d) n = 1 and R2is 5-NH2. The metal organic framework according to clause 1 or clause 2 comprising two organic ligands derived from a compound of Formula II, wherein a) in the first organic ligand derived from a compound of Formula II, n = 1 and R2is 3-NH2, and wherein in the second organic ligand derived from a compound of Formula II, n = 1 and R2is 3-CH3; b) in the first organic ligand derived from a compound of Formula II, n = 1 and R2is 3-NH2, and wherein in the second organic ligand derived from a compound of Formula II, n = 1 and R2is 5-CH3; c) in the first organic ligand derived from a compound of Formula II, n = 1 and R2is 5-NH2, and wherein in the second organic ligand derived from a compound of Formula II, n = 1 and R2is 3-CH3; or d) in the first organic ligand derived from a compound of Formula II, n = 1 and R2is 5-NH2, and wherein in the second organic ligand derived from a compound of Formula II, n = 1 and R2is 5-CH3. The metal organic framework according to any preceding clause comprising organic ligand derived from a compound of Formula III. The metal organic framework according to clause 7 wherein p = 1 and R3is selected from the group consisting of 4-Br, 4-NO2, 4-CH3, 5-Br, 4-C(O)OCH2CH3, 4-C(O)OCH3, and 4-CO2H. The metal organic framework according to clause 8 wherein p = 2, and wherein one R3is 4-Br and one R2is 5-Br. The metal organic framework according to any preceding clause, wherein in Formula I the CO2H is at the 4-position. The metal organic framework according to clause 10, wherein a) m = 0; b) m = 1 and R1is selected from the group consisting of 5-CF3, 3-NH2, 5-CH3, 5- CHF2, 5-CI, 3-CH3, and 3-CI; or c) m = 2 and one R1is 3-CH3 and one R1is 5-CH3.The metal organic framework according to any one of clauses 1 to 9, wherein in Formula I the CO2H is at the 3-position. The metal organic framework according to clause 12, wherein a) m = 0; b) m = 1 and R1is selected from the group consisting of 4-NH2, 4-Br, 4-NO2, 4-CF3, 5-CI, 5-CH3, 5-CH(CH3)2, 5-NH2, 5-Br, 5-C(O)CH3, 5-OH, 5-(4-methoxyphenyl), 5- CHF2, 5-CF3, 5-phenyl, 5-(4-nitrophenyl), 5-(4-fluorophenyl), 5-(3-nitrophenyl), 5-(2-methoxyphenyl), 5-(2,5-dimethoxyphenyl), 5-(3-chlorophenyl), and 5- (furan-2-yl); or c) m = 2 and wherein (i) one R1is 4-Br and one R is 5-CH3, (ii) both R1are linked to form a fused cycloalkane, preferably 1,4, 5, 6- tetrahydrocyclopentane[c]pyrazole-3-carboxylic acid, or (iii) both R1are linked to form a fused heterocycle, preferably l,4,6,7-tetrahydropyrano[4,3- c]pyrazole-3-carboxylic acid. The metal organic framework according to any one of clauses 1 to 9, wherein in Formula I the CO2H is at the 5-position. The metal organic framework according to clause 14, wherein a) m = 0; b) m = 1 and R1is selected from the group consisting of 4-1, 4-CI, 3-Br, 3- CH2CH2CH3, 3-NO2, 3-CH3, 3-hydroxymethyl, 4-Br, 3-C(CH3)3, 3-phenyl, 3-(4- hydroxyphenyl), 3-(2-fluorophenyl), and 3-(3-methoxyphenyl); or c) m = 2 and wherein (i) one R1is 3-NH2 and one R1is 4-Br, (ii) one R1is 3-Br and one R1is 4-CH3, (iii) one R1is 4-NH2 and one R1is 3-CH3, (iv) one R1is 4-NO2 and one R1is 3-CF3, or (v) both R1are CH3. The metal organic framework according to any preceding clause comprising organic ligand derived from the group consisting of lH-l,2,4-triazole, 2H-l,2,3-trizaole, 1H- 1,2,3-triazole, and combinations thereof, preferably comprising lH-l,2,4-triazole. The metal organic framework according to any preceding clause, wherein each metal ion of the plurality of metal ions is the ion of a metal independently selected from the group consisting of zinc, aluminium, indium, scandium, gallium, vanadium, zirconium, iron, copper, cobalt, magnesium, chromium, nickel, and manganese. The metal organic framework according to any preceding clause, wherein the composition comprises: from about 20% to about 50% metal ion by weight of the metal organic framework,from about 10% to about 50% organic ligand derived from compound of Formula I by weight of the metal organic framework, from about 10% to about 50% one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III by weight of the metal organic framework, and from about 0% to about 50% organic ligand derived from the group consisting of lH-l,2,4-triazole, 2H-l,2,3-triazole, lH-l,2,3-triazole, and combinations thereof, by weight of the metal organic framework. The metal organic framework according to any preceding clause, wherein the metal organic framework has a BET area of from about 500 m2 / g to about 1500 m2 / g, preferably from about 600 m2 / g to about 1200 m2 / g, preferably from about 700 m2 / g to about 1100 m2 / g, preferably from about 750 m2 / g to about 1000 m2 / g, preferably from about 800 m2 / gto about 925 m2 / g, preferably from about 850 to about 900 m2 / g. A metal organic framework body or bodies comprising metal organic framework as defined in clauses 1 to 19 and binder, preferably wherein the or each metal organic framework body comprises from about 1% to about 45% binder by weight of the or each metal organic framework body and from about 55% to about 99% metal organic framework by weight of the or each metal organic framework body. The or each metal organic framework body according to clause 20, wherein the or each metal organic framework body comprises from about 10% to about 35% binder by weight of the or each metal organic framework body. The or each metal organic framework body according to clause 20 or clause 21, wherein the binder is selected from the group consisting of polyvinyl alcohol (PVA), polyimide, polyamide, polyvinyl pyrrolidone, polycarboxylate and polyacrylate, polyurethane, polylactic acid and derivatives thereof, polysaccharides including cellulose-based polymers such as cellulose acetate, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose phthalate, and combinations thereof. The or each metal organic framework body according to clause 22, wherein the binder comprises a mixture of at least one cellulose-based polymer and / or PVA and at least one organic polymer selected from epoxide, polyacrylate and polyurethane. A metal-organic framework (MOF)-coated non-MOF substrate body or bodies, wherein the or each MOF-coated non-MOF substrate body comprises non- MOF substrate body(ies) and a MOF composition;wherein the MOF composition comprises MOF as defined in any one of clauses1 to 19; and wherein the external surface of the or each non-MOF substrate body is at least partially coated with MOF composition. A composition comprising metal organic framework as defined in any one of clauses 1 to 19, metal organic framework body or bodies as defined in any one of clauses 20 to23, MOF-coated non-MOF substrate body or bodies as defined in clause 24, or combinations thereof. A structured adsorbent bed comprising metal organic framework as defined in any one of clauses 1 to 19, metal organic framework body or bodies as defined in any one of clauses 20 to 23, MOF-coated non-MOF substrate body or bodies as defined in clause24, a composition as defined in clause 25, or combinations thereof. A method of producing metal organic framework as defined in any one of clause 1 to 19, the method comprising the steps of: a) providing a first solution comprising metal ion precursor, b) providing a second solution comprising organic ligand precursor derived from compound of Formula I, one or more further organic ligand precursors derived from compound selected from the group consisting of Formula II, Formula II, and combinations thereof, and optionally organic ligand precursor derived from the group consisting of lH-l,2,4-triazole, 2H-l,2,3-trizaole, 1H-1,2,3- triazole, or combinations thereof, and c) mixing the first solution and second solution to form metal organic framework. A method of producing metal organic framework as defined in any one of clauses 1 to 19, the method comprising the steps of: a) providing a first solution comprising one or more organic ligand precursors derived from compound of Formula I and one or more further organic ligand precursor derived from compound selected from the group consisting of Formula II, Formula III, and combinations thereof; b) providing a metal ion precursor, optionally in solid form; and c) contacting the metal ion precursor with the first solution form metal organic framework. Use of a metal organic framework as defined in any one of clauses 1 to 19, metal organic framework body or bodies as defined in any one of clauses 20 to 23, MOF- coated non-MOF substrate body or bodies as defined in clause 24, a composition as defined in clause 25, or a structured adsorbent bed as defined in clause 26 ina) carbon dioxide adsorption, preferably, high concentration carbon dioxide adsorption; b) water adsorption; c) catalysis; and / or d) gas separation.Examples

[0191] The invention will now be demonstrated by reference to the following non-limiting examples.

[0192] All reagents unless otherwise stated were obtained from commercial sources and were used without further purification.

[0193] Unless otherwise mentioned, herein room temperature and pressure are 21 °C (294.15 K, 69.8 °F) and 1 atm (14.696 psi, 101.325 kPa), respectively.Experimental MethodsMeasurement of Aspect Ratio (and Cross-Sectional Diameter)

[0194] The (largest and smallest) cross-sectional diameters and aspect ratio of the extrudates may be measured by dynamic image analysis. Suitable equipment is the Camsizer P4 from Microtrac MRB operated according to manufacturer's instructions. Such equipment has been shown to be comparable to a caliper measurement of a sample.

[0195] A sample, preferably >50 mL, is conveyed by a vibratory chute into the measurement zone where they pass in front of a planar light source in free fall. The resulting shadow projections are captured by a camera system and evaluated in real time. This allows the simultaneous measurement of the lengths and widths of the extrudates as well as their shape. The conveying along the vibratory chute helps align the extrudates for analysis.

[0196] The width of an extrudate is most conveniently defined as the smallest area bisector (XMa min -the smallest Martin diameter). This is viable even if the extrudate is bent or partially rounded. Extrudate length or Xstretch is conveniently defined as the square root of the product of the maximum Feret diameter (Xpemax) squared minus the minimum Martin diameter (XMa min) squared. The maximum Feret diameter (Xpemax) is the longest distance between two parallel lines touching the body projection.

[0197] The particle aspect ratio is therefore Xstretch / Xlvia min.

[0198] Equipment such as the Camsizer P4 will give a distribution of extrudate lengths (Xstretch) and widths (Xma min). The extrudate widths will be very monodispersed.

[0199] In the context of the disclosure, the mean aspect ratio will be understood by the skilled person to include the weight-based mean aspect ratio, or the volume-based mean aspect ratio, that is a mean aspect ratio characterised and defined from an aspect ratio distribution by weight, or volume, respectively. For example, the aspect ratio distribution may be a cumulative aspect ratio distribution, wherein the cumulative aspect ratio distribution is a fraction of bodies (based on weight, or volume) with aspect ratios less than a certain value. Preferably, the mean particle aspect ratio is a volume-based mean-particle aspect ratio.

[0200] The mean particle aspect ratio may be the "A50 aspect ratio" based on the volume- related cumulative distribution wherein 50% of the particles have an aspect ratio less than the A50 particle aspect ratio.Method for measuring the envelope density

[0201] The envelope density of a body can be measured by dividing the weight of a body (in grams) by its envelope volume (in mm3). The envelope volume is defined in ASTM D3766 as "the ratio of the mass of a particle to the sum of the volumes of the solid in each piece and the voids within each piece, that is, within close-fitting imaginary envelopes completely surrounding each piece". The envelope density of a body can be measured using techniques based on the Archimedes principle of volume displacement. For example, the envelopedensity can be measured by mercury porosimetry. At atmospheric pressure, mercury does not intrude into internal pores. Therefore, the volume of mercury displaced by a body at atmospheric pressure is the envelope volume of the body. Dividing the weight of the sample by this volume gives the envelope density. The use of mercury porosimetry is described above.

[0202] An alternative, and viable, technique for larger bodies, typically those with a diameter > 2 mm, is to use accurate 3-D scanners to measure the body volume. Suitable equipment includes the Leica BLK360. Preferably, powder pycnometers, such as the GeoPyc Model 1360 from Micrometrics Instrument Corp, can also be used to measure the envelope volumes and densities of bodies. If need be, the envelope volumes measured by these techniques can be used interchangeably with the envelope volume measured by mercury porosimetry.Method for Measuring Relative density

[0203] Relative density refers to the ratio of the envelope density of a crystalline adsorbent body compared to the crystal density of the adsorbent material.

[0204] The crystal density of a MOF is the density of a single crystal and is calculated theoretically from the structure. Structural and other information for MOFs, such as single crystal density, is theoretically calculated. Crystal density data is available from the Cambridge Structural Database at the Cambridge Crystallographic Centre.

[0205] Relative densities of much less than 1, such as less than 0.3, mean that there is excess porosity, mostly in the form of larger (hence less useful) pores in the body. Relative densities greater than 1 imply a wasteful loss of porosity as such high values can only be achieved by destroying some of the useful pores.Method of Measuring Bulk Density

[0206] The bulk density (tapped density) of the composition may be determined by loading a cylinder with a weighted amount of sample and tapping at least 50 times. The resulting volume of the packed material is then determined and the bulk density is calculated bydividing the sample weight by the sample volume. The diameter of the cylinder needs to be several times (>3) greater than the average length of any extrudates to allow packing. Cylinders of containers having a diameter of about 3 cm or greater are suitable. The depth of the packed bed also needs to be greater than about 3 cm to allow packing.

[0207] Due to the size and nature of the composition, only a limited amount of tapping or movement is required to pack the bodies efficiently. Increased amounts of tapping and different intensities of tapping, such as in some standards, do not significantly change the packing density.

[0208] The tapped density may be defined by methods such as the MPIF-46, ASTM B-527 or ISO 3953 tap density methods.Gas uptake

[0209]

[0243] N2 adsorption isotherm measurements were performed on a Micromeritics 3- Flex analyzer at 77 K (-196.15 °C). Around 80 mg samples were used for each measurement. Prior to the measurement, all the samples were degassed under vacuum at 120 °C for 24 hours using the internal turbopump. Gas uptakes were performed on the air-dried samples. The BET areas were calculated using BETSI as described in Osterrieth, J. W. M. et al., Advanced Materials, 2022, 34, 2201502.Method for determining the level of organic binder in an adsorbent body

[0210] The level of the organic binder in a MOF body can be determined by thermo- gravimetric methods based on weight loss at elevated temperatures. The high temperatures used (600°C) will burn off the organic species leaving metal oxide species etc behind. The difference in % weight loss between a sample of the adsorbent material and a sample of the adsorbent material plus binder shows the level of binder. The adsorbent body is crushed and a sample of the adsorbent body material is heated up to 600 °C and the weight loss when at steady state is measured and normalised. A sample of the adsorbent material is then heated under identical conditions and the weight loss normalised. The difference between the % wt losses is the % of binder present.

[0211] Residual solvent levels in a sample can be determined by weight loss of the sample after heating the sample to 120°C for 12 hours under vacuum. Binder level in the sample can then be determined by thermo-gravimetric analysis as previously described.Method of Measuring Micro-porosity and Meso-porosity

[0212] The micro and meso-porosity profile of a body can be determined by test method ASTM D4641-17. Suitable equipment for carrying out such tests is the 3Flex, from Micromeritics Corporation. The test method is as follows.

[0213] The test sample (0.5g) is typically heated to 120 °C under vacuum to remove adsorbed gases and vapours from the surface. The nitrogen adsorption branch of the isotherm is then determined by placing the sample under vacuum, cooling the sample to the boiling point of liquid nitrogen (~77.3 K), and then adding, in a stepwise manner, known amounts of nitrogen gas at increasing pressure P to the sample in such amounts that the form of the adsorption isotherm is adequately defined, and the saturation pressure of nitrogen is reached.

[0214] Each additional dose of nitrogen is introduced to the sample only after the preceding dose of nitrogen has reached adsorption equilibrium with the sample.

[0215] Typically, equilibrium is reached if the change in gas pressure is no greater than 0.1 torr / 5 min interval. This is continued until Po (the gas saturation pressure) is reached.

[0216] Data is typically plotted as the amount of gas adsorbed / desorbed (and derived porosity profiles) as a function of P / Po. The desorption isotherm is determined by desorbing nitrogen from the saturated sample in a stepwise manner with the same precautions taken to ensure desorption equilibration as those applied under adsorption conditions. Microporosity is associated with the volume of gas adsorbed at P / Po values of < 0.1 whereas mesoporosity is associated with the volume of gas adsorbed at P / Po values between 0.1 and 0.98.Method for measuring % MOF by weight in a MOF bodyThermo-gravimetric analysis (TGA) was used to determine the % binder and % MOF by weight in a MOF body. TGA experiments were carried out with a TGA550 (TA Instruments). The samples were heated from 20 °C to 650 °C at a ramp rate of 10 °C / min under nitrogen flow. Prior to analysing a MOF body, pristine binder and pristine MOF were analysed separately to record their decomposition temperature range. MOF body was then analysed and compared to the TGA profiles of pristine binder and MOF to obtain % binder and % MOF by weight of the MOF body. The TGA550 was operated according to the manufacturer's instructions.Method for measuring coating depth on MOF-coated substrate bodies

[0217] To evaluate the coating thickness and uniformity of the coating, scanning electron microscopy (SEM) imaging is performed using a TESCAN MIRA3 FEG-SEM (field emission gunscanning electron microscope) system, which is a high performance FEG-SEM system that features a high brightness Schottky emitter. Priorto coating the substrate is attached to carbon adhesive, sputter coated and a bridge of Cu tape added to join the coating to the pin stub. The TESCAN MIRA3 FEG-SEM is operated according to the manufacturer's instructions.Method for measuring water sorption

[0218] Water vapor sorption isotherms were measured on using a Surface Measurement Systems Dynamic Vapor Sorption Carbon (DVS-Carbon) system which gravimetrically measures the uptake and loss of vapour using nitrogen as a carrier gas. The water vapor sorption isotherm of a sample was measured using ca. 15 mg of the sample. Ultrapure water was used as the adsorbate for these measurements and the temperature was maintained at 25 °C or 70 °C as required by enclosing the system in a temperature-controlled incubator. The mass of the sample was determined by comparison to an empty reference pan and recorded by a high-resolution microbalance. Sorption isotherms were measured from 0% to 95% relative humidity stepwise. The samples were preactivated for overnight at 150 °C under nitrogen flow using a Micromeritics FlowPrep instrument and further activated at 150 °C for lh in situ before water sorption. The DVS-Carbon system and Micromeritics FlowPrep were operated according to the manufacturer's instructions.Method for measuring CO2 and N2 adsorption

[0219] Micromeritics 3-Flex was used to measure the CO2 and N2 gas sorption. Ultra-high- purity-grade CO2 and N2 were used for gas sorption measurements. Micromeritics 3-Flex surface-area and pore-size analyzer were used for all adsorption experiments (up to 1 bar). Single component gas-sorption experiments were performed on approximately 50 mg to 100 mg of activated MOF samples. To maintain a constant temperature throughout the duration of the experiment, a temperature-controlled bath was used. Samples were degassed on a Micromeritics FlowPrep instrument prior to the analysis by applying high temperature (150 °C) under N2 flow. The 3Flex and FlowPrep are operated according to the manufacturer's instructions.Materials and SynthesisSynthesis of I MM-33

[0220] To a screw-capped glass vial labelled "A", equipped with a magnetic stirrer, deionised water (5.69 mL and zinc carbonate basic (250.52 mg, 0.456 mmol) were added. The vial was placed in a heating block and heated gradually to 90 °C while stirring.

[0221] To another screw-capped glass vial labelled "B", equipped with a magnetic stirrer, 1H- pyrazole-4-carboxylic acid (127.78 mg, 1.14 mmol) and 3-methyl-lH-l,2,4-triazole (189.44 mg, 2.28 mmol) were added. Then deionised water (2.85 mL) and ethanol (2.85 mL) were added to vial B. The solution was stirred at room temperature until clear (10-15 minutes).

[0222] The solution in vial B was transferred into vial A. After the complete addition, the reaction mixture in vial A was stirred at 90 °C for 16 hours.

[0223] The reaction mixture was then cooled to room temperature. The resultant white colloidal solution was centrifuged using 50 mL centrifuge tubes at 4750 rpm for 20-30 minutes. After centrifugation, the supernatant was carefully removed without disturbing theMOF collected at the bottom. Methanol was added to the sediment, the mixture mixed well by shaking for a few seconds, and centrifuged again under the same conditions. The precipitate was allowed to sit in methanol overnight and washed once more with methanol before drying in air at room temperature. The MOF was activated at 150 °C under N2 flow for 7 hours. The yield of the MOF was 85%.Alternative IMM-33 synthesis

[0224] To a screw-capped vial equipped with a magnetic stirrer bar, was added 127.78 mg of lH-pyrazole-4-carboxylic acid (1.14 mmol), 189.44 mg of 3-methyl-lH-l,2,4-triazole (2.28 mmol), 2.85 mL of ethanol and 2.85 mL of deionized water. The vial was transferred to a heating block and gradually heated to 90°C with stirring. Once the material was completely dissolved, 250.52 mg of zinc carbonate basic (0.456 mmol) and 5.69 mL of deionized water was added to the vial. The reaction mixture was maintained at 90 °C for 16 h with stirring.

[0225] The reaction mixture was then allowed to cool to room temperature. The resulting white colloidal suspension of IMM-33 was centrifuged at 4750 rpm for 20-30 min using 50 mL centrifuge tubes. After centrifugation, the supernatant was carefully removed without disturbing the MOF collected at the bottom. Methanol was added to the sediment, the mixture mixed well by shaking for a few seconds, and centrifuged again under the same conditions. The precipitate was allowed to sit in methanol overnight and washed once more with methanol before drying in air at room temperature. The MOF was activated at 150 °C under N2 flow for 7 hours.Preparation of IMM-33 bodies

[0226] IMM-33 was prepared as described herein, however the 150 °C activation step was not carried out. Instead, following the final methanol wash, IMM-33 was dried and weighed. Methyl cellulose (20% by weight of the dried mass of IMM-33) was added and the mixture vortexed for 5 min to ensure thorough mixing. Vortexing was repeated three times and the mixture allowed to stand overnight (16 h). The mixture was vortexed once more and then heated at 30 °C overnight (16 h). The temperature was increased by 10 °C the next day andagain maintained overnight (16 h). This process was repeated to reach 70 °C. The mixture was maintained at 70 °C for 2-3 days to ensure complete drying and formation of IMM-33 bodies. The MOF bodies were then activated at 150 °C for 6 hours.

[0227] Solvent exchange of the obtained bodies prior to the activation step can be performed using methanol or ethanol by keeping the bodies submerged in methanol or ethanol for 2-3 days.Synthesis of I MM-34

[0228] To a screw-capped glass vial labelled "A", equipped with a magnetic stirrer, deionised water (5.69 mL) and zinc carbonate (250.52 mg, 0.456 mmol) were added. The vial was placed in a heating block and heated gradually to 90 °C while stirring.

[0229] To another screw-capped glass vial labelled "B", equipped with a magnetic stirrer, 1H- pyrazole-4-carboxylic acid (127.78 mg, 1.14 mmol) and 3-amino-lH-l,2,4-triazole (191.70 mg, 2.28 mmol) were added. Then deionised water (2.85 mL) and ethanol (2.85 mL) were added to vial B. The solution was stirred at room temperature until clear (10-15 minutes).

[0230] The solution in vial B was transferred into vial A. After the complete addition, the reaction mixture in vial A was stirred at 90 °C for 16 hours.

[0231] The reaction mixture was then cooled to room temperature. The resultant white colloidal solution was centrifuged using 50 mL centrifuge tubes at 4750 rpm for 20-30 minutes. After centrifugation, the supernatant was carefully removed without disturbing the MOF collected at the bottom. Methanol was added to the sediment, the mixture mixed well by shaking for a few seconds, and centrifuged again under the same conditions. The precipitate was allowed to sit in methanol overnight and washed once more with methanol before drying in air at room temperature. The MOF was activated at 150 °C under N2 flow for 7 hours.Alternative synthesis of I MM-34

[0232] To a screw-capped vial equipped with a magnetic stirrer bar, was added 127.78 mg of lH-pyrazole-4-carboxylic acid (1.14 mmol), 191.70 mg of 3-amino-lH-l,2,4-triazole (2.28 mmol), 2.85 mL of ethanol and 2.85 mL of deionized water. The vial was transferred to a heating block and gradually heated to 90°C with stirring. Once the material was completely dissolved, 250.52 mg of zinc carbonate basic (0.456 mmol) and 5.69 mL of deionized water was added to the vial. The reaction mixture was maintained at 90 °C for 16 h with stirring.

[0233] The reaction mixture was then allowed to cool to room temperature. The resulting white colloidal suspension of IMM-34 was centrifuged at 4750 rpm for 20-30 min using 50 mL centrifuge tubes. After centrifugation, the supernatant was carefully removed without disturbing the MOF collected at the bottom. Methanol was added to the sediment, the mixture mixed well by shaking for a few seconds, and centrifuged again under the same conditions. The precipitate was allowed to sit in methanol overnight and washed once more with methanol before drying in air at room temperature. The MOF was activated at 150 °C under N2 flow for 7 hours.Preparation of IMM-34 bodies

[0234] IMM-34 was prepared as described herein, however the 150 °C activation step was not carried out. Instead, following the final methanol wash, IMM-34 was dried and weighed. Methyl cellulose (15% by weight of the dried mass of IMM-34) and polyacrylate (15% by weight of the dried mass of IMM-34) was added and the mixture vortexed for 5 min to ensure thorough mixing. Vortexing was repeated three times and the mixture allowed to stand overnight (16 h). The mixture was vortexed once more and then heated at 30 °C overnight (16 h). The temperature was increased by 10 °C the next day and again maintained overnight (16 h). This process was repeated to reach 70 °C. The mixture was maintained at 70 °C for 2-3 days to ensure complete drying and formation of IMM-34 bodies. The MOF bodies were then activated at 150 °C for 6 h.

[0235] Solvent exchange of the obtained bodies prior to the activation step can be performed using methanol or ethanol by keeping the bodies submerged in methanol or ethanol for 2-3 days.Synthesis of I MM-35

[0236] To a screw-capped glass vial labelled "A", equipped with a magnetic stirrer, deionised water (5.69 mL) and zinc carbonate (250.52 mg, 0.456 mmol) were added. The vial was placed in a heating block and heated gradually to 90 °C while stirring.

[0237] To another screw-capped glass vial labelled "B", equipped with a magnetic stirrer, 1H- pyrazole-4-carboxylic acid (127.78 mg, 1.14 mmol), 3-methyl-lH-l,2,4-triazole (94.72 mg, 1.14 mmol), lH-l,2,4-triazole (70.86 mg, 1.026 mmol) and 3-amino-lH-l,2,4-triazole (9.58 mg, 0.114 mmol) were added. Then deionised water (2.85 mL) and ethanol (2.85 mL) were added to vial B. The solution was stirred at room temperature until clear (10-15 minutes).

[0238] The solution in vial B was transferred into vial A. After the complete addition, the reaction mixture in vial A was stirred at 90 °C for 16 hours.

[0239] The reaction mixture was then cooled to room temperature. The resultant white colloidal solution was centrifuged using 50 mL centrifuge tubes at 4750 rpm for 20-30 minutes. After centrifugation, the supernatant was carefully removed without disturbing the MOF collected at the bottom. Methanol was added to the sediment, the mixture mixed well by shaking for a few seconds, and centrifuged again under the same conditions. The precipitate was allowed to sit in methanol overnight and washed once more with methanol before drying in air at room temperature. The MOF was activated at 150 °C under N2 flow for 7 hours.Alternative synthesis of I MM-35

[0240] To a screw-capped vial equipped with a magnetic stirrer bar, was added 127.78 mg of lH-pyrazole-4-carboxylic acid (1.14 mmol), 94.72 mg 3-methyl-lH-l,2,4-triazole (1.14 mmol),70.86 mg lH-l,2,4-triazole (1.026 mmol), 9.58 mg 3-amino-lH-l,2,4-triazole (0.114 mmol), 2.85 mL of ethanol and 2.85 mL of deionized water. The vial was transferred to a heating block and gradually heated to 90°C with stirring. Once the material was completely dissolved, 250.52 mg of zinc carbonate basic (0.456 mmol) and 5.69 mL of deionized water was added to the vial. The reaction mixture was maintained at 90 °C for 16 h with stirring.

[0241] The reaction mixture was then allowed to cool to room temperature. The resulting white colloidal suspension of IMM-35 was centrifuged at 4750 rpm for 20-30 min using 50 mL centrifuge tubes. After centrifugation, the supernatant was carefully removed without disturbing the MOF collected at the bottom. Methanol was added to the sediment, the mixture mixed well by shaking for a few seconds, and centrifuged again under the same conditions. The precipitate was allowed to sit in methanol overnight and washed once more with methanol before drying in air at room temperature. The MOF was activated at 150 °C under N2 flow for 7 hours.Preparation of IMM-35 bodies

[0242] IMM-35 was prepared as described herein, however the 150 °C activation step was not carried out. Instead, following the final methanol wash, IMM-35 was dried and weighed. Methyl cellulose (20% by weight of the dried mass of IMM-35) was added and the mixture vortexed for 5 min to ensure thorough mixing. Vortexing was repeated three times and the mixture allowed to stand overnight (16 h). The mixture was vortexed once more and then heated at 30 °C overnight (16 h). The temperature was increased by 10 °C the next day and again maintained overnight (16 h). This process was repeated to reach 70 °C. The mixture was maintained at 70 °C for 2-3 days to ensure complete drying and formation of IMM-35 bodies. The MOF bodies were then activated at 150 °C for 6 h.

[0243] Solvent exchange of the obtained bodies prior to the activation step can be performed using methanol or ethanol by keeping the bodies submerged in methanol or ethanol for 2-3 days.

[0244] Figure 1 shows the 21 °C CO2 adsorption isotherm analysis of the MOFs. All the three MOFs shows open isotherms with higher uptake at 1 bar, while IMM-34 shows higher uptakes both at 0.15 bar and 1 bar, respectively. Without wishing to be bound by theory, it is belived that the shape of the isotherms indicates that the MOFs of the invention exhibit low hear of adsorption resulting in improved regenerability. The following table shows the CO2 uptake of the MOFs at 0.15 bar (15 kPa) and 1 bar (100 kPa) measured at 21 °C.

[0245] Figure 2(a) shows the 77K N2 adsorption isotherm analysis for the MOFs and Figure 2(b) shows the 21 °C N2 adsorption isotherm analysis for IMM-34. This shows that the BET surface areas of IMM-33, IMM-34 and IMM-35 are 735 m2 / g, 797 m2 / g and 906 m2 / g, respectively.

[0246] Figure 3 shows the powder X-ray diffraction (PXRD) analysis of the MOFs. The PXRD pattern indicates that IMM-33 and IMM-35 can be isoreticular while IMM-34 may have a different structure. The thermogravimetric (TGA) analysis of IMM-33 and IMM-35 (Figure 4) shows that the MOFs are thermally stable up to 350 °C before linker degradation resulting in structure disintegration begins.

[0247] While IMM-33 and IMM-35 display type 1 isotherms with higher uptake due to their open structures, IMM-34 exhibits an S-shaped water isotherm, indicating its hydrophobic nature (Figure 5). This hydrophobic characteristic of IMM-34 can be attributed to its unique structure, as suggested by PXRD analysis, which may be due to the lH-pyrazole-4-carboxylic acid linker, known from literature to form hydrophobic architectures. As indicated by variabletemperature water adsorption, the hydrophobic nature of IMM-34 increases slightly when water adsorption is measured at 70 °C. (Figure 6).

[0248] Figure 7 shows the 21 °C CO2 adsorption analysis of IMM-33, IMM-34 and IMM-35 before and after exposure to 99% relative humidity for 1 week at room temperature. The 21 °C CO2 adsorption analysis demonstrates that the MOF is stable in presence of moisture.

[0249] Figure 8 shows the room temperature CO2 (15% CO2 concentration) adsorption isotherm analysis of the IMM-33, IMM-34 and IMM-35 powder compared to MOF powders CALF-20, UTSA-16 and ZU-301.

[0250] Figure 9 shows the water sorption of IMM-33, IMM-34 and IMM-35 powders compared to MOF powders UTSA-16 and ZU-301 at 25 °C and 70 °C.

[0251] Figure 10 shows the room temperature CO2 (15% CO2 concentration) adsorption isotherm analysis of IMM-33, IMM-34 and IMM-35 bodies compared to MOF bodies UTSA-16 and ZU-301.

[0252] Figure 11 shows the long term steam stability of IMM-34 body when exposed to steam at 140 °C over 4 weeks, at 1 week intervals. IMM-34 body demonstrates robust stability, maintaining porosity and mechanical integrity even after exposure to steam for 4 weeks.

[0253] Figure 12 shows the long term stability of IMM-34 body when exposed to 70% relative humidity for 4 weeks (15% CO2 / 85% N2). These results show that IMM-34 body exhibits similar CO2 adsorption uptake and behaviour before and after exposure to humidity. Figure 13 demonstrates the stability of IMM-34 body under acidic conditions (pH 5 solution of H2SO4 for 24 h). IMM-34 body is stable and maintains its porosity and mechanical stability.

Claims

Claims1. A metal organic framework (MOF) comprising(i) a plurality of metal ions, each of the plurality of metal ions having a valency selected from the group consisting of +2 and +3; and(ii) a plurality of organic ligands, the plurality of organic ligands comprising a) organic ligand derived from a compound of Formula I;b) one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III; andc) optionally, organic ligand derived from the group consisting of 1H- 1,2,4-triazole, 2H-l,2,3-trizaole, lH-l,2,3-triazole, and combinations thereof; wherein each R1is independently selected from the group consisting of Cl, Br, I, F, CF3, CHF2, R4, NH2, substituted amino, Cl, Br, I, NO2, C(O)R4, OH, aryl, substituted aryl; wherein each R2and each R3is independently selected from the group consisting of Br, Cl, I, F, CF3, CHF2, NH2, substituted amino, NO2, R4, CO2R4, CO2H, CONH2, SH, and CN; wherein R4is Ci to C4 alkyl or substituted Ci to C4 alkyl; wherein m = 0, 1 or 2 wherein n = 1 or 2; and wherein p = 1 or 2.

2. The metal organic framework according to claim 1 comprising organic ligand derived from a compound of Formula II.

3. The metal organic framework according to claim 1 or claim 2 wherein n = 1 and R2is selected from the group consisting of 3-CI, 3-1, 3-NH2, 5-NH2, 3-Br, 5-Br, 3-CO2H, 3-CN, 3-C(O)NH2, 3-CO2CH3, 5-CO2CH2CH3, 3-CH3, 5-CH3, 3-CH2CH3, 5-CH2CH3, 3-CHF2, 3- CF3, 5-CF3, 3-SH, 3-NO2, and 5-NO2.

4. The metal organic framework according to claim 1 or claim 2 wherein n = 2, and wherein (i) one R2is 3-NH2 and one R2is 5-NH2, (ii) one R2is 3-CI and one R2is 5-CI, (iii) one R2is 3-Br and one R2is 5-Br, (iv) one R2is 3-CH3 and one R2is 5-CH3, (v) one R2is 3-CN and one R2is 5-NH2, (vi) one R2is 3-C(O)OCH3 and one R2is 5-NH2, (vii) one R2is 3-SH and one R2is 5-CH3, (viii) one R2is 3-NH2 and one R2is 5-SH, (ix) one R2is 3- C(O)OCH3 and one R2is 5-Br, (x) one R2is 3-CO2H and one R2is 5-Br, (xi) one R2is 3- C(O)OCH2CH3 and one R2is 5-CI, (xii) one R2is 3-SH and one R2is 5-CF3, (xiii) one R2is 3-CO2H and one R2is 5-NH2, or (xiv) one R2is 3-NH2 and one R2is 5-CO2H.

5. The metal organic framework according to claim 1 or claim 2, comprising one organic ligand derived from a compound of Formula II, wherein(i) n = 1 and R2is 3-CH3;(ii) n = 1 and R2is 3-NH2;(iii) n = 1 and R2is 5-CH3; or(iv) n = 1 and R2is 5-NH2.

6. The metal organic framework according to claim 1 or claim 2 comprising two organic ligands derived from a compound of Formula II, wherein(i) in the first organic ligand derived from a compound of Formula II, n = 1 and R2is 3-NH2, and wherein in the second organic ligand derived from a compound of Formula II, n = 1 and R2is 3-CH3;(ii) in the first organic ligand derived from a compound of Formula II, n = 1 and R2is 3-NH2, and wherein in the second organic ligand derived from a compound of Formula II, n = 1 and R2is 5-CH3;(iii) in the first organic ligand derived from a compound of Formula II, n = 1 and R2is 5-NH2, and wherein in the second organic ligand derived from a compound of Formula II, n = 1 and R2is 3-CH3; or(iv) in the first organic ligand derived from a compound of Formula II, n = 1 and R2is 5-NH2, and wherein in the second organic ligand derived from a compound of Formula II, n = 1 and R2is 5-CH3.

7. The metal organic framework according to any preceding claim comprising organic ligand derived from a compound of Formula III.

8. The metal organic framework according to claim 7 wherein p = 1 and R3is selected from the group consisting of 4-Br, 4-NO2, 4-CH3, 5-Br, 4-C(O)OCH2CH3, 4-C(O)OCH3, and 4-CO2H.

9. The metal organic framework according to claim 8 wherein p = 2, and wherein one R3is 4-Br and one R2is 5-Br.

10. The metal organic framework according to any preceding claim, wherein in Formula I the CO2H is at the 4-position.

11. The metal organic framework according to claim 10, wherein(i) m = 0;(ii) m = 1 and R1is selected from the group consisting of 5-CF3, 3-NH2, 5-CH3, 5- CHF2, 5-CI, 3-CH3, and 3-CI; or(iii) m = 2 and one R1is 3-CH3 and one R1is 5-CH3.

12. The metal organic framework according to any one of claims 1 to 9, wherein in Formula I the CO2H is at the 3-position.

13. The metal organic framework according to claim 12, wherein(i) m = 0;(ii) m = 1 and R1is selected from the group consisting of 4-NH2, 4-Br, 4-NO2, 4-CF3, 5-CI, 5-CH3, 5-CH(CH3)2, 5-NH2, 5-Br, 5-C(O)CH3, 5-OH, 5-(4-methoxyphenyl), 5- CHF2, 5-CF3, 5-phenyl, 5-(4-nitrophenyl), 5-(4-fluorophenyl), 5-(3-nitrophenyl), 5-(2-methoxyphenyl), 5-(2,5-dimethoxyphenyl), 5-(3-chlorophenyl), and 5- (furan-2-yl); or(iii) m = 2 and wherein (a) one R1is 4-Br and one R is 5-CH3, (b) both R1are linked to form a fused cycloalkane, preferably 1, 4,5,6- tetrahydrocyclopentane[c]pyrazole-3-carboxylic acid, or (c) both R1are linked to form a fused heterocycle, preferably l,4,6,7-tetrahydropyrano[4,3- c]pyrazole-3-carboxylic acid.

14. The metal organic framework according to any one of claims 1 to 9, wherein in Formula I the CO2H is at the 5-position.

15. The metal organic framework according to claim 14, wherein(i) m = 0;(ii) m = 1 and R1is selected from the group consisting of 4-1, 4-CI, 3-Br, 3- CH2CH2CH3, 3-NO2, 3-CH3, 3-hydroxymethyl, 4-Br, 3-C(CH3)3, 3-phenyl, 3-(4- hydroxyphenyl), 3-(2-fluorophenyl), and 3-(3-methoxyphenyl); or(iii) m = 2 and wherein (a) one R1is 3-NH2 and one R1is 4-Br, (b) one R1is 3-Br and one R1is 4-CH3, (c) one R1is 4-NH2 and one R1is 3-CH3, (d) one R1is 4-NO2 and one R1is 3-CF3, or (e) both R1are CH3.

16. The metal organic framework according to any preceding claim comprising organic ligand derived from the group consisting of lH-l,2,4-triazole, 2H-l,2,3-trizaole, 1H- 1,2,3-triazole, and combinations thereof, preferably comprising lH-l,2,4-triazole.

17. The metal organic framework according to any preceding claim, wherein each metal ion of the plurality of metal ions is the ion of a metal independently selected from the group consisting of zinc, aluminium, indium, scandium, gallium, vanadium, zirconium, iron, copper, cobalt, magnesium, chromium, nickel, and manganese.

18. The metal organic framework according to any preceding claim, wherein the composition comprises: from about 20% to about 50% metal ion by weight of the metal organic framework, from about 10% to about 50% organic ligand derived from compound of Formula I by weight of the metal organic framework, from about 10% to about 50% one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III by weight of the metal organic framework, and from about 0% to about 50% organic ligand derived from the group consisting of lH-l,2,4-triazole, 2H-l,2,3-triazole, lH-l,2,3-triazole, and combinations thereof, by weight of the metal organic framework.

19. The metal organic framework according to any preceding claim, wherein the metal organic framework has a BET area of from about 500 m2 / g to about 1500 m2 / g, preferably from about 600 m2 / g to about 1200 m2 / g, preferably from about 700 m2 / g to about 1100 m2 / g, preferably from about 750 m2 / g to about 1000 m2 / g, preferably from about 800 m2 / g to about 925 m2 / g, preferably from about 850 to about 900 m2 / g.

20. A metal organic framework body or bodies comprising metal organic framework as defined in any one of claims 1 to 19 and binder, preferably wherein the or each metal organic framework body comprises from about 1% to about 45% binder by weight of the or each metal organic framework body and from about 55% to about 99% metal organic framework by weight of the or each metal organic framework body.

21. A metal-organic framework (MOF)-coated non-MOF substrate body or bodies, wherein the or each MOF-coated non-MOF substrate body comprises non- MOF substrate body(ies) and a MOF composition;wherein the MOF composition comprises MOF as defined in any one of claims 1 to 20; and wherein the external surface of the or each non-MOF substrate body is at least partially coated with MOF composition.

22. A composition comprising metal organic framework as defined in any one of claims 1 to 19, metal organic framework body or bodies as defined in claim 20, MOF-coated non-MOF substrate body or bodies as defined in claim 21, or combinations thereof.

23. A structured adsorbent bed comprising metal organic framework as defined in any one of claims 1 to 19, metal organic framework body or bodies as defined in claim 20, MOF- coated non-MOF substrate body or bodies as defined in claim 21, a composition as defined in claim 22, or combinations thereof.

24. A method of producing metal organic framework as defined in any one of claims 1 to 19, the method comprising the steps of:(i) providing a first solution comprising metal ion precursor,(ii) providing a second solution comprising organic ligand precursor derived from compound of Formula I, one or more further organic ligand precursors derived from compound selected from the group consisting of Formula II, Formula II, and combinations thereof, and optionally organic ligand precursor derived from the group consisting of lH-l,2,4-triazole, 2H-l,2,3-trizaole, 1H-1,2,3- triazole, or combinations thereof, and(iii) mixing the first solution and second solution to form metal organic framework.

25. Use of a metal organic framework as defined in any one of claims 1 to 19, metal organic framework body or bodies as defined in claim 20, MOF-coated non-MOF substrate body or bodies as defined in claim 21, a composition as defined in claim 22, or a structured adsorbent bed as defined in claim 23 in(i) carbon dioxide adsorption, preferably, high concentration carbon dioxide adsorption;(ii) water adsorption, preferably water harvesting or heating, ventilation and air conditioning (HVAC);(iii) catalysis;(iv) a gas separation process, preferably the gas separation process may be selected from the group consisting of carbon dioxide capture, krypton recovery, krypton purification, and combinations thereof;(v) removing CO2 directly from the flue gas of an industrial process;(vi) separation of Kr from a mixture of Kr / CF Nz, to obtain pure Kr from a mixture of Kr, CF4 and N2;(vii) hydrogen storage; and / or(viii) hydrocarbon purification.

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